United States Patent (11) 3,632,391

72) Inventors Robert E. Whitfield 3,233,962 2/1966 Nelson...... 17162.2 X Pleasant Hill; 3,318,727 5/1967 Boenig. 1 7/62.2 X Allen G. Pittman, El Cerrito; William L. Wasley, Berkeley, all of Calif. FOREIGN PATENTS 21 Appl. No. 805,379 957,564 2/1957 Germany...... 22 Filed Mar. 7, 1969 Primary Examiner-William D. Martin 45) Patented Jan. 4, 1972 Assistant Examiner-David Cohen 73 Assignee The United States of America as Attorneys-R. Hoffman, W. Bier and W. Takacs represented by the Secretary of Agriculture Original application May 12, 1967, Ser. No. 655,695, now Patent No. 3,440,002, ABSTRACT: Fibrous materials (e.g., wool, cotton, viscose, which is a division of application Ser. No. etc.) carrying a deposit of a preformed polymer containing 371,150, May 28, 1964, now Patent No. functional groups, which is cross-linked in situ through reac 3,372,978. Divided and this application tion with a fixative containing functional groups complemen Mar. 7, 1969, Ser. No. 805,379 tary to those on the polymer. Typically, the functional groups on the polymer are carbonyl halide, haloformate, isocyanate, anhydride, or carbamyl halide groups. In such case, the func 54 TREATMENT OF TEXTILE MATERIALS tional groups on the fixative may be amino or hydroxyl groups. 28 Claims, No Drawings Alternatively, the polymer may contain amino or hydroxyl groups, in which case the fixative would contain carbonyl ha 52 U.S. Cl...... 117/62.2, lide, haloformate, isocyanate, anhydride, or carbamyl groups. 1 171126 AB, 117/126GB, 1171138.8 F, 1171138.8 Various types of polymers may be employed including addi UA, 177138.8 E, 177138.8 N, 1171138.8D, tion polymers and copolymers, and condensation polymers 1 17/140A, 117/141, 1171142, 117/143 A such as polyesters, polyamides, and polyethers. The novel 5) Int. Cl...... B44d 1/44 products are made by processes which utilize a phase bounda (50 Field of Search...... 1 17162. 1, ry limited reaction. One embodiment thereof is to form the 62.2, 14, 142, 143 A, 148, 155 R, 155 UA, 145, complementary agents (the preformed polymer and fixative) 126 GB, 126 AB, 138.8 F, 138.8 UA, 138.8 E, into separate solutions in mutually immiscible solvents, these 138.8 N, 138.8D, 140 A, 161 P, 161 K, 1 solutions then being applied serially to the fibrous material. 56) References Cited Alternatively, a solution of one of the agents in a volatile sol vent is applied to the substrate, which is then dried to remove UNITED STATES PATENTS solvent, and the complementary agent is then applied in fluid 3, 152,920 10/1964 Caldwell et al...... 1 17162.2X form, e.g., as a vapor or dissolved in a solvent which is not 3,156,579 1 1/1964 Baldwin et al...... 17162.2 necessarily immiscible with the first solvent. 3,632,391 2 TREATMENT OF TEXTLE MATER ALS substrate are modified by applying thereto a preformed This application is a division of our application Ser. No. polymer and cross-linking it to form a three-dimensional 655,695, filed May 12, 1967, now U.S. Pat. No. 3,440,002, structure, the cross-linking being accomplished by reaction of which in turn is a division of our application Ser. No. 371,150, the preformed polymer and the fixative at a phase boundary. filed May 28, 1964, now U.S. Patent No. 3,372,978. In a typical embodiment of the invention, wool is first im A nonexclusive, irrevocable, royalty-free license in the pregnated with an aqueous solution of the fixative, e.g., a invention herein described, throughout the world for all diamine such as hexamethylene diamine. The wool is then im purposes of the United States Government, with the power pregnated with a solution of a preformed polymer in a water to grant sublicenses for such purposes, is hereby granted to immiscible solvent such as carbon tetrachloride. The polymer the Government of the United States of America. 10 may be, for example, a copolymer of ethylene and A principal object of this invention is the provision of new methacryloyl chloride, containing at least three COC1 groups methods for treating fibrous materials, particularly textiles. per molecule. By serial application of these solutions to the Another object of the invention is the provision of the novel fabric, each fibrous element is coated with a two-phase products so produced. Further objects and advantages of the system, for example, an inner layer of diamine in water and an invention will be obvious from the following description 15 outer layer of the highly reactive polymer in water-immiscible wherein parts and percentages are by weight unless otherwise solvent. Under these conditions, the diamine and the polymer specified. The symbol d is used throughout to designate the react almost instantaneously at the boundary between the Structure. phases, producing in situ on the fibera cross-linked, insoluble, resin coating. By suitable selection of the complementary reactants, a wide variety of polymeric, fiber-modifying agents In the processing of fibrous materials, e.g., textiles, it is can be cross-linked in situ on fibers. It is to be particularly often desired to modify the inherent properties of the materi noted that no heat-curing step is needed-the serial applica als, for example, to improve their shrinkage characteristics, to tion of the reactants is all that is necessary. The critical feature increase their resistance to soiling, to enhance their softness, 25 in this regard is that we provide a phase boundary-limited etc. Various procedures have been advocated for such pur system whereby the cross-linking takes place directly-as poses and they usually involve applying to the fibrous sub soon as the reactants are applied-and hence there is no need strate an agent having the chemical structure required to ef for heat curing to promote the reaction. fect the desired modification of the fibers. Such agents In the patents of Miller et al. 3,078,138 and Whitfield et al. which may be generically termed fiber-modifying agents-are 30 3,079,216, 3,079,217, 3,084,018 3,084,019 and 3,093,441 generally polymers of any of various classes, for example, there are disclosed processes wherein linear condensation polyethylene, polypropylene, or other polyolefines, polymers-e.g., polymides-are formed in situ on fibrous sub chlorosulphonated polyethylenes; polyvinylpyrrollidones; strates by polymerizing complementary bifunctional polymer polyepoxides; formaldehyde-melamine resins; vinyl polymers; intermediates in an interfacial system. Thus in a typical em starch and starch derivatives, etc. Ordinarily, application of 35 bodiment thereof, wool is first impregnated with an aqueous the polymer with nothing more yields at best a temporary af solution of a diamine and then impregnated with a solution of fect; the polymer is removed when the treated fibers are sub a diacid chloride in a water-immiscible solvent such as carbon jected to laundering or dry cleaning. To attain a more lasting tetrachloride. Under these conditions, polymerization takes effect, it is conventional to apply the polymer in conjunction place at the interface between the mutually immiscible phases, with an agent-commonly termed a fixative or curing agent 40 producing in situ a linear polyamide. in order to cause a cross-linking of the molecules of the Although the procedures of the aforesaid patents provide polymer rendering it insoluble in water and dry-cleaning sol very useful and practical results and are indeed in commercial vents. A universal feature of such procedures is that they use, they inherently possess certain limitations. The procedure require a curing operation at elevated temperatures to attain of the present invention does not have these limitations and, the desired insolubilization of the polymer. A typical 45 moreover, provides results are not obtainable by the prior procedure of this type is disclosed by Bruner et al. (U.S. Pat. techniques. These points are further explained as follows: No. 2,678,286) who apply a solution containing (a) 1. A fundamental item is that the patented procedure util chlorosulphonated polyethylene and (b) a fixative such as izes an interfacial system to build a polymer from small units hexamethylenediamine or 3-methoxyhexamethylene diamine so that the procedure may accurately be termed interfacial to wool and then cure the treated wool at 150° C. for 50 polymerization and is so referred to hereinafter. On the other anywhere from 2 to 10 minutes. Such heat curing steps entail hand, the present procedure starts with a preformed polymer serious disadvantages. For one thing, they impede production and utilizes an interfacial system to cross-link it. Thus, the by tying up large amounts of material. For example, in textile present procedure may be considered as involving interfacial mills processing is conducted at rates of at least 25 yards per cross-linking of a preformed polymer. The distinction is not minute and it is obvious that if a heat cure of 10 minutes is 55 just a matter of words but involves basic and important required, 250 yards of material will constantly be tied up in distinctions. A vital point is that the patented system forms the curing oven, hence not available for use or sale. Other dis linear polymers. Bifunctional polymer-forming monomers are advantages are the expense of the heating equipment, main applied and a linear polymer is produced on the surface of the tenance of the auxiliary devices such as guides, rollers, etc., substrate. In contrast, in the present procedure a preformed and the cost of fuel. A further point is that heating at curing 60 linear polymer is initially applied as the primary reactant. The temperatures often is detrimental to the fibrous material, reaction which then occurs at the phase boundary is a cross causing such deleterious changes as yellowing, loss in tensile linking of this preformed polymer; that is, individual strength and abrasion resistance, and other changes attributa molecules of the original polymer are joined to another, form ble to degradation of the fiber molecules. Wool is a typical ex ing a three-dimensional structure. ample of a fiber which is readily yellowed and degraded by ex 65 These distinctions are further demonstrated by the follow posure to elevated temperatures, particularly when in contact ing illustrative formulas: with alkaline substances, e.g., curing agents containing amino (a) Interfacial polymerizations groups. A particular feature of the present invention is that essen tially permanent modifications of fiber properties are attained 70 ex sh Seb - a tex Seb Hex Seb Hex Seb Hex Sob . . . . without any heat-curing step. As a result, the invention yields hexamethylene sebacoyl linear polymar containing the advantages of rapid and simple operation, decreased cost of production, and avoidance of fiber yellowing and degrada diamine chloride alternating units derived from hexamethylene diamine tion. 75 in accordance with the invention, the properties of a fibrous and sebacoyl chloride

I 3,632,391 3 4 (b) In accordance with the invention: a polymer which is three-dimensional, hence inherently in Solubie. Moreover, if grafting does occur, one attains a dou ... EEEEEEEEEEEEEEEEEEM o e ble-anchoring effect in that both the grafting and the cross Preformed linear polyner linking contribute to the permanence of the fiber modifica of ethylene and tion. To sum up the situation, grafting is essential in the prior ethacryloyl chloride 4. examethylene diamine procedure where permanence of modification is required. In CE ethylene uait, M as accordance with the present invention, permanence of fiber methacryloyl chloride unit) modification is attained by cross-linking a preformed polymer. Grafting, if it does occur, serves to reinforce the durability of 10 yields the modification. 4. Another item is that the interfacial polymerization procedure by its very nature yields polymers wherein polar M- . . . . groups (amide, urea, urethane, ester or carbonate groups) s recur along the polymer chain in relatively close spacing. For 4. 3. 5 R example, polyhexamethylene sebacamide (produced by 3. P 3 polymerizing hexamethylene diamine and sebacoyl chloride in 0. & situ on a fibrous substrate) will contain an amide group EEEEEEEEEEMEEEEEE-et-M Croas-linked 3-dimaa Ek sional) structure 20 (-C-NII-)s containing polymer . . . . . EEE EEEEEEME EEEEE-sex--- chains of ethylete and recurring after each group of six or eight carbon atoms. Such E. ethacryloyl unita, polarity may be undesirable, for example, in instances where it ex R is intended that the treated fibers display a high degree of linked through hexa 25 hydrophobicity. On the contrary, the process of the present in E. tyiee diac t vention does not necessarily yield such highly polar products as a EEEEEEMEEEEEEMEEEEEE . . . . methylene 18 and, in fact, one can readily form cross-linked polymers which contain very lengthy chains completely free from polar radi er Bes cals. Typically, this can be done by applying a polymer con 30 taining long hydrocarbon chains such as those of MEEEEEMEEEEEEEEEEEE polyethylene, polypropylene, polybutylene, etc. The resulting cross-linked polymer will contain very long carbon chains between polar groups; indeed, these carbon chains may con Since linear polymers contain independent chains, whereas tain anywhere from 25 or 50 to hundreds of carbon atoms. cross-linked polymers contain interconnected chains, substan 35 tial distinctions in properties are displayed by the two forms of COMPONENTA polymers. For example, linear polymers are soluble in organic solvents; they are fusible and display typical thermoplastic (THE PREFORMED POLYMER) properties, i.e., they flow when heated. Cross-linked (ther 40 In the practice of the invention, selection is made of the ap mosetting) polymers are insoluble in organic solvents and at propriate complementary agents to provide the desired most are swelled thereby. Also, they are not fusible and do not modification of the fibers. These complementary agents will exhibit plastic properties when heated, i.e., they do not flow. comprise a preformed polymer (hereinafter termed com 2. The interfacial polymerization system is limited to the ponent A) and the fixative or cross-linking agent (hereinafter formation of condensation polymers, i.e., polyamides, polyu 45 termed component B). rethanes, polyureas, polyesters, polycarbonates, and inter As noted hereinabove, the invention is of wide versatility polymers containing various combinations of amide, urethane, and a multitude of different substances may be used as com urea, ester, or carbonate groups. In contrast, the procedure of ponent A. Basically, component A may be any polymer which the present invention is not so limited. One can apply all kinds contains highly reactive groups and which is soluble in water of polymers-not only condensation polymers but also addi 50 or in organic solvents such as alcohol, acetone, hydrocarbons, tion polymers. As a matter of fact, the present invention is of or chlorinated hydrocarbons, etc. From a structural view particular advantage for the very reason that one can apply point, component A is a linear polymer, with or without addition polymers, for example, polyolefines, polyacrylates, branching, which possesses the above critical characteristics. polyperfluoroacrylates, polyvinyls, and the like. Addition It is preferred that component A have a molecular weight of at polymers have the benefits that they are readily available, 55 least 1000 to provide adequate film-forming and fiber-modify relatively inexpensive, and, most importantly, offer a very ing ability. The characteristic of solubility is desired so that the wide spectrum of physical and chemical properties for the polymer can be uniformly applied to fibrous substrates in the modification of the fibrous substrate. This last item is illus form of a solution. The highly reactive groups are required to trated by the following examples: Application of elastomers provide the sites for the eventual cross-linking of component such as chlorosulphonated polyethylene to confer such at 60 tributes as enhanced resiliency; polystyrene polymers to A in the phase boundary system. The expression "highly reac confer stiffness; perfluoracrylates to provide resistance to soil tive group' is employed herein to designate a functional radi ing; etc. It is important to note at this point that addition cal which on contact with a complementary functional radical polymers cannot be formed by the aforesaid interfacial under interfacial conditions will combine therewith rapidly polymerization technique; monomers required to form addi 65 and directly without requiring any after treatments such as tion polymers will not polymerize under the conditions in oven cures. Because of the facility with which these groups question at any practical rate. react on contact, they may also be termed contact-responsive 3. In the interfacial polymerization system, permanency of or contact-effective functional groups. It is essential that there fiber modification is attained only if the polymer becomes be at least two, preferably at least three, of these highly reac grafted to the fiber molecules. If the characteristics of the sub 70 tive groups per polymer molecule. For best results it is strate are such that no grafting occurs, the polymer deposit is preferred that the number of highly reactive groups be corre but temporary and is removed by such influences as launder lated with molecular weight of the polymer, employing a ing, dry-cleaning, mild abrasion, etc. However, in the process greater number as the polymer molecular weight is increased. of the present invention grafting is not an essential factor. Per Illustrative examples of highly reactive groups which may be manence of modification depends on the fact that the applied 75 present are carbonyl halide (-COX), sulphony halide (- polymer is cross-linked (by reaction with the fixative) to form SOX); haloformate (-OCOX); carbamyl halide (-NH 3,632,391 5 6 COX); isocyanate (-NCO); anhydride Allyl and methallyl esters of fatty acids, e.g., allyl and (-g o-g ); imide ( g-NH ); amine (-NH); methallyl acetates, propionates, butyrates, valerates, capry lates, caprates, laurates, myristates, palmitates, stearates, O. O. O O oleates, etc. imine (-N-); and hydroxy 5 N-Dialkyl acrylamides and N-dialkyl a-substituted acryla (-OH). In the above formulas X stands for a halogen, i.e., mides, for example, N-dimethyl, N-diethyl, N-dipropyl, N fluorine, chlorine, bromine, or iodine. The sulphur analogues dibutyl, N-diamyl, N-dihexyl, N-dioctyl, N-didodecyl, etc., of any of the above oxygen-containing species, e.g., -CSC1, acrylamides, methacrylamides, ethacrylamides, propacryla -SCOC1, -SCSC1, -OCSC, -NCS, -SH, etc., are also mides, etc. included within the ambit of the invention. The several highly O Olefinic hydrocarbons and halogenated olefinic hydrocar reactive groups of component A may be all the same or may bons such as ethylene, propylene, butylene, isoprene, bu be of different species. For example, the reactive groups may tadiene, styrene, chloroprene, a-methylstyrene, dimethyl be two or more carbonyl chloride groups; two or more styrene, vinyl naphthalene, dichlorostyrenes, vinyl chloride, sulphonyl chloride groups; two or more amine groups; one vinyl bromide, vinylidene chloride, vinylidene bromide, vinyl carbonyl chloride group and one or more sulphonyl chloride 15 fluoride, etc. groups; one amino group and one or more hydroxyl groups; Ketones such as methyl vinyl ketone, ethyl vinyl ketone, one chloroformate group and one or more carbonyl chloride isopropyl vinyl ketone and other alkyl vinyl ketones, methyl groups, etc. Other combinations of two or more different spe isopropylketone, methyl alkyl ketone, etc. cies of reactive groups will be evident from the above. Itaconic diesters, for example, the dimethyl, diethyl The expression "acid halide group' is used herein as gener 20 diisopropyl, dibutyl, dihexyl, didodecyl, and other dialkyl ic to carbonyl halide, sulphony halide, haloformate, and car esters of itaconic acids. Diaryl and diaralkyl esters of itaconic bamyl halide groups. acid, e.g., diphenyl itaconate, dibenzyl itaconate, di-(phen Illustrative types of polymers which may be employed as ylethyl)itaconate, etc. Other compounds containing the typical component A are given below: 25 COMPONENTA (ADDITION POLYMERS) CH=CK Basically, this embodiment of component A may be con grouping such as cyanostyrenes, vinyl thiophene, vinyl sidered as an addition polymer which contains pendant highly pyridine, vinyl pyrrole, acrylonitrile, methacrylonitrile, alkyl reactive groups of the types described above. Typically, these 30 vinyl sulphones such as ethyl vinyl sulphone. Compounds of substances are prepared by copolymerizing two types of un the types: saturated monomeric materials, namely, a first ingredient used in major proportion (e.g., about 55 to 95 mole percent of the R R copolymerization system) and a second ingredient used in / CH=C-O-CH-CH-N- minor proportion (about 5 to 45 mole percent of the 35 N copolymerization system). Generally, the first ingredient is R1 provided to contribute to the copolymer the desired high R. O. R molecular weight and also to contribute to the polyner the ul / timate properties desired to be imparted to the fibrous sub CH-C-C-O-CH-CH-N strate in the cross-linking procedure. The second ingredient 40 R1 provides the pendant, highly reactive groups. R. O. R. R Typical examples of monomers which may be used as the / major ingredient are: Cir-c-c-N-CI-CH-N Alkyl esters of acrylic acid and alkyl esters of any of the R1. various o-alkylacrylic or a-haloacrylic acids, e.g., the methyl, 45 ethyl, propyl, isopropyl, butyl, amyl, hexyl, octyl, decyl, where R is H or CHa and wherein R is a lower alkyl group dodecyl, tetradecyl, hexadecyl, octadecyl, cyclohexyl, oleyl, such as Cha, CH5, etc. etc., esters of acrylic, methacrylic, ethacrylic, propacrylic, Vinyl ethers, for example, monomers of the type CH, CH chloracrylic, bromoacrylic, etc., acids. O-R wherein R is an alkyl radical such as methyl, ethyl, Aryl and aralkyl esters of acrylic acid or the a-substituted 50 propyl, butyl, benzyl, etc. acrylic acids, e.g., phenyl, o-, m-, p-tolyl, dodecylphenyl, In many cases, it is preferred that the major ingredient be a benzyl, phenylethyl, etc., esters of acrylic, methacrylic, fluorine-containing monomer. Copolymers produced ethacrylic, propacrylic, chloroacrylic, bromoacrylic, etc., therefrom are useful to impart such characteristics to the acids. fibrous substrates as resistance to both oil- and water-borne Alkyl acrylates or methacrylates containing an oxygen 55 soils. Typical illustrative examples of fluorine-containing bridge, typically methoxyethyl acrylate, ethoxyethyl acrylate, monomers are: perfluoro-t-buytl acrylate, perfluoro-t-butyl propoxyethyl acrylate, butoxyethyl acrylate, octoxyethyl acry methacrylate, and esters of the type late, cyclohexoxyethyl acrylate, benzoxyethyl acrylate, phenoxyethyl acrylate, methoxyethyl methacrylate, phenox yethyl methacrylate, etc. 60 II-(CF-CF)-CH-O-C- Acrylates containing such radicals as thioether, sulphone, or sulphoxide, for example, the esters of acrylic acid or wherein R is H or CH and n is an integer from 2 to 6. Typical methacrylic acid with alcohols of the types: examples of this type of primary perfluoralkyl ester are: 1,2,5- trihydroperfluoropenty acrylate and methacrylate, 1, 1,7- R-S-CH-CH-OH 65 trihydroperfluoroheptyl acrylate and methacrylate, 1, 19 trihydroperfluorononyl acrylate and methacrylate, 1,1,1 1 R-SO-CH-CH-OH trihydroperfluoroundecyl acrylate and methacrylate, 1,1,13 R-SO-CH-CH-OH trihydroperfluorotridecyl acrylate and methacrylate, etc. Usually, it is preferred that the fluoroalkyl radical contain at wherein R is an alkyl radical such as methyl, ethyl, propyl, bu 70 least 3 fluorine atoms and an especially desirable type of tyl, etc., or an aryl or aralkyl radical such as phenyl, tolyl, fluoroalkyl ester for the multipurpose treatment mentioned benzyl, phenylethyl, etc. above is one wherein the fluoroalkyl radical not only contains Vinyl esters of fatty acids, e.g., vinyl acetate, propionate, at least three fluorine atoms but also has its omega carbon butyrate, valerate, caprylate, caprate, laurate, myristate, pal atom completely fluorinated. Typical of these particularly mitate, stearate, oleate, etc. 75 preferred fluoroalkyl esters are those of the type 3,632,391 8 O R R C H=(- SOX wherein R is H or CH and n is an integer of from 0 to 8. Illus R trative examples of such compounds are the acrylic and CII-C-e- SOX methacrylic acid esters of 1,1-dihydroperfluoropropyl al cohol, 1,1-dihydroperfluorobutyl alcohol, 1,1-dihydroper wherein R and X are as defined in (l) above. fluorohexyl alcohol, l, 1-dihydroperfluorooctyl alcohol, 1,1- 3. Unsaturated monomers containing carboxylic acid or dihydroperfluorodecyl alcohol, 1,1-dihydroperfluorododecyl sulphonic acid groups, for example alcohol, 1,1-dihydroperfluorohexadecyl alcohol, O 1, dihydroperfluorooctadecyl alcohol, etc. R Another useful type of fluorine-containing monomer com CH--C OOM prises the compounds of the structure R 5 CB-C-s OM R CH-)--cooM wherein R is a saturated fluorocarbon structure containing from four to 18 fully fluorinated carbon atoms, R' is hydrogen R or an alkyl group containing from one to six carbon atoms and 20 CH-5-a-s OM R' is hydrogen or a methyl group. Typical examples of par ticular compounds in this area are: N-methyl, N-perfluorobu wherein R is as defined in (1) above and wherein M is Horan tanesulfonyl acrylamide; N-methyl, N-perfluorobutanesulfo alkali metal. nyl methacrylamide, N-perfluoro(2-methylcyclohexane)sulfo Copolymers made with these sulphonic- or carboxylic-con nyl methacrylamide; N-methyl, N-perfluoro(4-methyl 25 taining monomers may be converted to the corresponding cyclohexane)sulfonyl acrylamide; N-propyl, N-perfluoro(2- acid halide forms by, for example, reaction with a thionyl ha methylcyclohexane)sulfonyl methacrylamide; N-perfluorooc lide, phosphorus trichloride, or the like. tanesulfonyl acrylamide; N-perfluorooctanesulfonyl 4. Unsaturated monomers containing an isocyanate or methacrylamide; N-ethyl, N-perfluorooctanesulfonyl acryla isothiocyanate group, for example, compounds of the types mide, N-isobutyl, N-perfluoro(4-ethylcyclohexane)-sulfonyl 30 acrylamide; N-isobutyl, N-perfluorodecanesulfonyl R methacrylamide, N-propyl, N-perfluorododecanesulfonyl CH-C-NCY acrylamide; N-(n-hexyl), N-perfluorooctadecanesulfonyl acrylamide. i In cases where it is desired to impart water repellency to the 35 CH=C-CH-NCY fibrous substrate, one may employ as the major ingredient un saturated monomers containing silicon. Typical in this catego I ry are the acryloxymethyl (or methacryloxymethyl) deriva CH=C-C-O-R-NCY tives of organic silanes or polysiloxanes, for example, com R pounds of the types 40 CH=C-d-NCY wherein R is as defined in (1) above, R' is a bivalent radical R-Si-CH-O--c- CH such as ethylene or other alkylene radical or a phenylene group etc., and Y is O or S. k k 45 5. Unsaturated monomers containing an anhydride or imide R. R. group as, for example, maleic anhydride or imide, itaconican R-Si-O-Si-CH-O C-C = CH: hydride or imide, etc. 6. Unsaturated monomers containing free amino groups or R R R - hydroxyl groups, for exampie, compounds of the types wherein R is hydrogen or methyl and the R's are monovalent 50 organic radicals, typically alkyl groups containing one to 18 R carbon atoms, cyclohexyl, phenyl, toluy, benzyl, diphenyl, or CH-C-OH-OH the like. Typical examples of compounds in this category are R acryloxymethyl trimethylsilane, methacryloxymethyl trimethylsilane, acryloxymethyl dimethylphenylsilane, 55 CH-C-CH-NHR methacryloxymethyl dimethylphenylsilane, acryioxymethyl R. O pentamethyldisiloxane, methacryloxymethyl pentamethyldis CH-C-E-O-R-OH iloxane, etc. Illustrative examples of the minor ingredient are as follows: R. O. 1. Unsaturated monomers containing a carbonyl halide 60 CH-C-E-O-R-NHR group, e.g., compounds of the formula R R. O. CH---OH R 65 wherein R is hydrogen, an alkyl group such as methyl, ethyl, CH-c-e-NHR propyl, butyl, phenyl, etc., and wherein X is C, Br, For I. wherein R is as defined in ( ) above and R' is as defined in (4) above. Styrene derivatives of the type 7. Unsaturated monomers containing a haloformate or car 70 bamyl halide group, for example CH2=C-p-COXR R CH-C-CH-0 COX wherein X and R are as defined above 2. Unsaturated monomers containing a sulphonyl halide R group, e.g., compounds of the formulas 75 city--CH-NH-C (OX 3,632,391 9 O R. O 1 || terephthalic, hexahydrophthalic, maleic, and the like. By CH-C-C-O-R-O COX suitable adjustment of the proportions of reactants in known manner, the polyesters will contain free hydroxy groups. The R. O. resulting polyesters can be employed directly as component CII-C-C-O-R-NH-COX A, utilizing the free hydroxy groups as the highly reactive i groups. Another plan is to react the hydroxylated polyethers CH=C--O COX with a diacid chloride (or bischloroformate) to provide a polyether containing free carbonyl chloride (or chloroformate R groups). In this connection, typical reactants are succinyl Cl=C-b-NHCOX chloride, adipyl chloride, pimelyl chloride, sebacyl chloride, phthalyl chloride, ethylene glycol bischloroformate, wherein R and X are as defined in (l) above and wherein R' is diethylene glycol bischloroformate, hexane-1,6-diol as defined in (4) above. bischloroformate, and the like. As well known in the art, the 15 polyester and diacid chloride (or bischloroformate) are em COMPONENTA ployed in such proportion as to provide a COCl/OH (or (CONVERTED ADDITION POLYMERS) OCOCl/OH) ratio of more than one to one whereby to ensure that the product contains free carbonyl chloride or chlorofor If desired, one may prepare addition polymers essentially mate groups. In a preferred form of the invention, one uses free from highly reactive groups and then subject them to 20 polyesters containing free isocyanate groups. Such polymers known reactions to introduce the necessary highly reactive can be readily prepared by reacting the hydroxylated groups. An example in this area is the chlorosulphonation of polyester with a diisocyanate. Typical examples of the diiso polyoflefines such as polyethylene or polypropylene by reac cyanates are o-, M-, or p-phenylene diisocyanate, toluene 2,4- tion with SO, and Cl. This introduces chloro groups and (or 2,6-) diisocyanate, metaxylylene diisocyanate, 3,5,3',5'- sulphonyl chloride (-SOCl) groups into the polymer. 25 bixylylene-4,4'-diisocyanate, etc. As well known in the art, the Another example is the partial hydrolysis of vinyl ester or vinyl diisocyanate and polyester are employed in such proportion as ether polymers, to introduce hydroxyl groups into the polymer to provide an NCO/OH ratio of more than one to one whereby chain. Another example is a copolymer containing carboxy to ensure that the product contains free NCO groups. groups which are then converted into carbonyl halide groups Products of this type are sometimes referred to in the art as by reacting the copolymer with such agents as thionyl 30 polyurethanes because they contain internal urethane groups, chloride, phosphorus trichloride, or the like. formed through combination of hydroxy groups of the COMPONENTA polyester with isocyanate groups of the diisocyanate reactant. COMPONENT A (POLYETHERS) (CONDENSATION POLYMERS) 35 Component. A need not necessarily be an addition polymer; Polyethers derived, for example, by polymerizing an oxide one may use condensation polymers of all types. Although (or epoxide, as they are often termed) with a polyhydric al some investigators employ the term "condensation polymer' cohol such as ethylene glycol, propylene glycol, trimethylene only in respect to polymers wherein a low molecular weight glycol, glycerol, pentaerythritol, sorbitol, trimethylolpropane, byproduct (such as HO or HCl) is split out during polymer 40 etc. Generally, the polyethers are derived from the simple al formation, we employ the term in the broader and accepted kylene oxides such as ethylene oxide or propylene oxide but sense as designating any polymer which contains interunit one may also use such compounds as butylene oxide, isobu functional groups not present in the monomers. Thus, we in tylene oxide, trimethylethylene oxide, dodecylene oxide, hex clude such types as polyalkyleneimines, polyurethanes, polyu adecylene oxide, tetramethylethylene oxide, a-methylstyrene reas, etc., whose formation is not ordinarily accompanied by 45 oxide, styrene oxide, cyclopentene epoxide, cyclohexene any byproduct elimination. Various types of condensation epoxide, vinyl cyclohexene epoxide, butadiene monoepoxide, polymers which may be used in the practice of the invention naphthyl ethylene oxide, dipentene epoxide, 1,2-epoxy-2,4,4- are listed in the following paragraphs by way of illustration but trimethyl pentane (diisobutylene epoxide), 1,1-diphen not limitation. ylethylene oxide, epifluorhydrin, epichlorhydrin, epibrom 50 hydrin, 1,1,1-trifluoro-2-propylene oxide, 1,1,1-trifluoro-1- COMPONENT A methyl-2-propylene oxide, 1,1,1-trifluoro-2-butene oxide, 1,1,1,2,2,3,3-heptafluoro-4-hexene oxide, hexylglycidyl ether, (POLYALKYLENE IMINES) allylglycidyl ether, phenylglycidyl ether, 2-chloroethylglycidyl A useful class of polymers which can be used as component ether, o-chlorophenylglycidyl ether, methacrylchloride epox A are the polyalkylene imines. A special feature of these is 55 ide, 3-chloro-1,2-epoxybutane glycidol, methyl 9,10-epox that they have built-in reactive groups on the polymer ystearate, 3,4-epoxycyclohexyl cyanide, 2-methyl-2,3-epox backbone, namely, internal imine (-NH-groups and ter yhexanol, etc. The resulting polyethers can be employed minal amine (-NH) groups. Typical examples are the directly as component A, utilizing the free hydroxy groups as polymers of ethylene imine, propylene imine, 1,2-butylene 60 the highly reactive groups. In such case, it is preferred that the imine, 2,3-butylene imine, 2,2-dimethyl ethylene imine, 2,2,3- polyethers contain at least 3 hydroxy groups per molecule, ob trimethyl ethylene imine, 2,2-dimethyl-3-propyl ethylene tainable by utilizing a polyhydric alcohol containing at least 3 imine, cyclohexyl ethylene imine, phenyl ethylene imine, etc. hydroxy groups in the polymerization with the oxide These compounds, as well known in the art, can be prepared, monomer. Another plan is to react the hydroxylated polyether for example, by polymerizing the alkylene innine monomer in 65 with a diacid chloride (or bischloroformate) to provide a the presence of a catalyst such as sodium bisulphite, polyether containing free carbonyl chloride (or chloroformate hydrochloric acid, sulphuric acid, acetic acid, hydrogen groups). In this connection, typical reactants are succinyl peroxide, etc. Generally, it is preferred to use the polyalkylene chloride, pimelyl chloride, sebacyl chloride, phthalyl chloride, imines which are at least partially soluble in water. ethylene glycol bischloroformate, diethylene glycol 70 bischloroformate, hexane-1,6-diol bischloroformate, and the COMPONENT A (POLYESTERS) like. As well known in the art, the polyether and diacid Polyesters derived from polyols such as ethylene glycol, chloride (or bischloroformate) are employed in such propor propylene glycol, trimethylene glycol, hexamethylene glycol, tions as to furnish a COCl/OH (or OCOCl/OH) ratio of more glycerol, pentaerythritol, sorbitol, trimethylolpropane, etc., than one to one whereby to ensure that the product contains and dibasic acids such as succinic, adipic, sebacic, phthalic, 75 free carbonyl chloride or chloroformate groups. In a preferred 3,632,391 11 2 form of the invention, one uses polyethers containing free iso R. cyanate groups. Such polymers can be readily prepared by -si-o- reacting the hydroxylated polyether with a diisocyanate. Typi R cal examples of the diisocyanates which may be reacted with the polyethers are o-, m-, or p-phenylene diisocyanates, toluene 2,4- (or 2,6-) diisocyanate, metaxylylene diiso wherein R is a monovalent organic radical such as alkyl con cyanate, 3,5,3',5'-bixylylene-4,4'-diisocyanate, 3,3'- taining one to 18 carbon atoms, phenyl, benzyl, toluyl, biphen bitolylene diisocyantate, diphenylmethane-4,4'-diisocyanate, yl, cyclohexyl, or the like, R' is an alkylene group containing, naphthalene-1,5-diisocyanate, etc. As well known in the art, the diisocyanate and polyether are employed in such propor 10 for example, two to 0 carbon atoms, and Q is OH, NH2, tions as to provide an NCO/OH ratio of more than one to one COCl, NCO or other highly reactive group as disclosed herein. whereby to ensure that the product contains free isocyanate Also typical are copolymers containing a multiplicity of units groups. These products are sometimes referred to as polyu of the types rethanes because they contain internal urethane groups, 15 R R formed through the combination of hydroxy groups of the - s i-O and -i-o- polyether with isocyanate groups of the diisocyanate reactant. k R COMPONENTA (POLY AMIDES) d The polyamides used in accordance with the invention are 20 those derived from polyamines and polybasic acids. Methods wherein R, R', and Q are as above. The polymers or of preparing these polyamides by condensation of polyamines copolymers may be modified to introduce selected highly and polycarboxylic acids are well known in the art and need reactive groups. For example, polymers or copolymers con not be described here. One may prepare polyamides contain taining free OH or NH groups may be reacted with an excess ing free amino groups or free carboxylic acid groups. 25 of a diisocyanate, such as toluene diisocyanate, to provide a Generally, it is preferred to employ polyamides which contain siloxane with free isocyanate groups. Similarly, polymers or free amino groups. The polyamides may be derived from such copolymers containing free OH or NH groups may be reacted polyamines as ethylene diamine, diethylene triamine, with an excess of a diacid chloride or a bischloroformate-for triethylene tetramine, tetraethylene pentamine, i,4-diamino 30 example, adipoyl chloride or ethylene glycol bischlorofor butane, 1,3-diaminobutane, hexamethylene diamine, 3-(N- mate-to produce a siloxane containing free carbonyl isopropylamino) propylamine, 3,3'-imino-bispropylamine, chloride or chloroformate groups. and the like. Typical polycarboxylic acids which may be con Other class of condensation polymers usable as component densed with the polyamines to form polyamides are glutaric A are: polymers containing free amine or isocyanate groups acid, adipic acid, pimelic acid, suberic acid, azelaic acid, 35 prepared by copolymerizing a diamine such as hexamethylene sebacic acid, isophthalic acid, terephthalic acid, betamethyl diamine with a diisocyanate such as toluene diisocyanate, adipic acid, 1,2-cyclohexane dicarboxylic acid, malonic acid, Polycarbonates containing free hydroxy or chloroformatic polymerized fat acids, and the like. Depending on the amine groups, prepared by copolymerizing a polyol such as and acid constituents and conditions of condensation, the bisphenol A with ethylene glycol bischloroformate. Polycar polyamides may have molecular weights varying about from 40 bonates containing free hydroxy groups may be reacted with 1,000 to 10,000 and melting points about from 20-200 C. diisocyanates, as described hereinabove in connection with Particularly preferred for the purpose of the invention are the the polyesters, to provide a polycarbonate containing free iso polyamides derived from aliphatic polyamines and polymeric cyanate groups. fat acids. Such products are disclosed, for example, by Cowan et al., U.S. Pat. No. 2,450,940. Typical of these polyamides 45 COMPONENT B (THE FIXATIVE) are those made by condensing ethylene diamine or diethylene Component B may be any compound containing at least two triamine with polymeric fat acids produced from the highly reactive groups. As to these groups, the same choice is polymerization of drying or semidrying oils, or the free acids, available as set forth hereinabove in connection with com or simple aliphatic alcohol esters of such acids. The polymeric ponent A and thus they may typically be of the following fat acids may typically be derived from such oils as soybean, 50 types: Carbonyl halide (-COX), sulphonyl halide (-SOX), linseed, tung, perilla, oiticica, cottonseed, corn, tall, sun haloformate (-OCOX), carbamyl halide (-NHCOX), an flower, safflower, and the like. As well known in the art, in the hydride polymerization the unsaturated fat acids combine to produce a mixture of dibasic and higher polymeric acids. Usually the (-i-o-g- inide (--NH-g- mixture contains a preponderant proportion of dimeric acids 55 O s O O with lesser amounts of trimeric and higher polymeric acids, and some residual monomeric acid. Particularly preferred are amine (-NH), imine (-NH-), hydroxy (-OH), iso the polyamides of low melting point (about 20°-90° C.) con cyanate (-NCO). In the above formulas, X stands for F, Cl, taining free amino groups which may be produced by heating Br, or I. The sulphur analogues of any of the above oxygen together an aliphatic polyamine, such as diethylene triamine, 60 containing species, e.g., -CSCI, -SCOCl, -SCSC, - triethylene tetramine, 1,4-diaminobutane, tetraethylene pen OCSCl, -NCS, -SH, etc., are also included within the ambit tamine, 1,3-diaminobutane, and the like, with the polymerized of the invention. fat acids. Typical among these is a polyamide derived from The several reactive groups of component B may be all of diethylene triamine and dimerized soybean fatty acids. 65 the same species or of different species. For example, the reactive groups may be two or more carbonyl chloride groups; COMPONENTA two or more sulphonyl chloride groups, two or more amine groups; one carbonyl chloride group and one or more (OTHER CONDENSATION TYPES) sulphonyl chloride groups; one amine group and one or more 70 hydroxyl groups; etc. Other combinations of two or more dif A useful class of condensation polymers, particularly where ferent species of reactive groups will be evident from the it is desired to impart such qualities as shrink resistance, water above illustrations. repellency, resistance to water-borne soils, etc., are the it is, of course, obvious that in a practice of the invention polysiloxanes. Typical are the polymers containing a mul one selects components A and B so that they contain reactive tiplicity of siloxane units of the structure 75 groups which are in a complementary relation, that is, which 3,632,391 13 14 are reactive with one another, whereby the desired cross-link using compounds containing two - COCl groups one may use ing will take place. The following table illustrates how one compounds containing one -CSC and one -COCl group or may select the reactive groups on the respective components compounds containing two -CSCI groups. Moreover, A and B to ensure that they are in complementary (reactive) although the carbonyl chlorides are preferred as they are reac relationship: 5 tive and relatively inexpensive, the corresponding fluorides, bromides, and iodides may be used. Complementary Reactive Groups It is generally preferred to use the aliphatic compounds con taining two carbonylchloride groups in alpha, omega posi tions, particularly those of the type: Reactive group Complementary reactive group 10 on one component (A or B) on complementary component Cl CO-(CH)CO Cl (B or A) wherein n has a value from 2 to 12. Another preferred catego ry includes the compounds of the formula CICO-A-COCl Carbonylhalide Amine, innine, hydroxy (where A is the benzene or cyclohexane radical), especially Sulfonylhalide Amine, imine, hydroxy para-substituted compounds such as terephthalyl and hex Haloformate Amine, imine, hydroxy 15 ahydroterephthalyl chlorides. Carbamyl halide Amine, imine, hydroxy Amine, inninc, or hydroxy Carbonylhalide, sulfonyl COMPONENTB (FIXATIVE) CONTAININGSOX halide, haloformate, carbamyl halide, isocyanate, GROUPS isothiocyanate, anhydride Isocyanate or isothiocyanate Amine, imine, or hydroxy 20 Typically, one may employ compounds of the aliphatic, aro Anhydride or imide Amine, imine, or hydroxy matic, and heterocyclic series containing at least two sulphon yl halide (-SOX) groups. The compounds may be sub stituted if desired with noninterfering (nonfunctional) groups We generally prefer to employ systems wherein one com such as ether groups, thioether groups, sulphone groups, etc. ponent carries carbonyl halide, haloformate, or isocyanate 25 Typical compounds in this category are listed below by way of groups and the other component carries groups containing ac illustration and not limitation: benzene-1,3-disulphonyl tive hydrogen atoms, i.e., hydroxy, amine, or imine groups. Of chloride, benzene-1,4-disulphonyl chloride, naphthalene-1,5- these, amine and imine groups are particularly preferred as disulphonyl chloride, naphthalene-2,7-disulphonyl chloride, providing especially rapid cross-linking. Systems with iso biphenyl-4,4'-disulphonyl chloride, hexane-1,6-disulphonyl cyanates and amines (or imines) offer the special benefit that 30 chloride, cyclohexane-1,4-disulphonyl chloride, ethane-l,2- the cross-linking does not produce any byproducts, e.g., no disulphonyl chloride, toluene disulphonyl chloride, p,p'-ox hydrogen halide as in the acid halide-amine systems. ybis (benzenesulphonyl chloride), and compounds of the type Since the goal of the phase boundary-limited reaction is to wherein X is F, Cl, Br, or I and n has a value from 2 to 12. cross-link the preformed polymer (component A), it is neces 35 sary that each of the components A and B contain at least two COMPONENTB (FIXATIVE) CONTAINING OCOX reactive groups and, moreover, that the sum of the groups be GROUPS five or more. For example, if the selected component A con tains two of the highly reactive groups, component B should Typically, one may employ compounds of the aliphatic, aro contain no less than three of the complementary reactive 40 matic, or heterocyclic series containing at least two halofor groups. If the selected component A contains three of the mate (-OCOX) groups. The compounds may be substituted reactive groups, it is evident that component B may contain as if desired with noninterfering (nonfunctional) substituents few as two of the complementary groups. MOreover, as the such as sulphone groups, ether groups, thioether groups, etc. molecular weight of component A is increased, it is preferred Typical examples of compounds in this category are listed that the sum of the reactive groups be more than five to assure 45 below merely by way of illustration and not limitation: the proximity of complementary reactive groups during the ethylene glycol bischloroformate, diethylene glycol cross-linking reaction. bischloroformate, 2,2-dimethyl propane 1,3-diol bischlorofor Illustrative examples of compounds which may be used as mate, propane-1,3-diol bischloroformate, butane-1,4-diol component B are listed below: bischloroformate, hexane-1,6-diol bischloroformate, octane 50 1,8-diol bischloroformate, decane-1,10-diol bischloroformate, COMPONENTB (FIXATIVE) CONTAINING COX butane-1,2-diol bischloroformate, hexane-1,2-dio GROUPS bischloroformate, 2-methoxyglycerol-1,3-bischloroformate, glycerol-1,2-bischloroformate, glycerol-1,3-bischloroformate, Typically, one may employ compounds of the aliphatic, aro diglycerol bischloroformate, hexanetriol bischloroformate, matic, or heterocyclic series containing at least two carbonyl pentaerythritol bischloroformate, cyclohexane-1,4-diol halide (-COX) groups. The compounds may be substituted if bischloroformate, hydroquinone bischloroformate, resorcinol desired with noninterfering (nonfunctional) substituents such bischloroformate, catechol bischloroformate, bischlorofor as ether groups, thioether groups, sulphone groups, etc. Typi mate of 2,2-bis(parahydroxyphenyl) propane, bischlorofor cal examples of compounds in this category are listed below mate of 2,2-bis(parahydroxyphenyl)butane, bischloroformate merely by way of illustration and not limitation: phosgene, ox 60 of 4,4'-dihydroxybenzophenone, bischloroformate of 1,2- alyl chloride, maleyl chloride, fumaryl chloride, malonyl bis(parahydroxyphenyl) ethane, naphthalene-1,5-diol chloride, succinyl chloride, glutaryl chloride, adipyl chloride, bischloroformate, biphenyl-4,4'-diol bischloroformate, pimelyl chloride, suberyl chloride, azelayl chloride, sebacyl glycerol trichloroformate, pentaerythritol tetrachloroformate, chloride, cyclohexane-1,4-biscarbonyl chloride, phthalyl and the like. If desired, mixtures of different bishaloformates chloride, isophthalyl chloride, terephthalyl chloride, 4,4'- 65 may be used. biphenyldicarbonyl chloride, g-hydromuconyl chloride, i.e., Among the preferred compounds are the aliphatic Cl CO-CH-CH CH-CH-CO Cl, diglycollic acid bischloroformates, for example, those of the type: chloride, i.e., O(CH-COCl), higher homologues of this compound as O(CH-CH-COCl), dithiodiglycollic acid chloride, diphenylolpropanediacetic acid chloride, i.e., 70 O O (CH),C(CHO CH, CO Cl), trimellityl chloride, i.e., CCO-(CH)n-OC Cl CH(COCl), and the like. If desired, mixtures of different carbonyl halides may be used. It is also evident that the wherein in has a value from 2 to 12. Another preferred catego sulphur analogues of these compounds may be used and are ry of compounds are the bis-chloroformates derived from included within the spirit of the invention. Thus, instead of 75 polyethylene glycols, e.g.,

a ra

3,632,391 1S 16 O toluylene diamine, ortho-tolidine, piperazine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, 3,3'- C-C-O-CH-CH-Io CH-CH-)-O CH-CH-of-ch imino-bispropyl amine, 6,6'-imino-bishexyl amine, pen wherein n has a value from zero to 10. A useful category of taerythrity amine, and the like. If desired, mixtures of the aromatic bischloroformates are the bisphenol chloroformates, amines or imines may be used. It is generally preferred to use that is, compounds of the type: aliphatic alpha, omega diamines, particularly of the type HN-(CH)-NH R wherein n has a value of 2 to 12, preferably 6 to 10. Another preferred class is compounds of the type CO CO ? -O CO Cl 10 R. R. R. - wherein n is 2, 3, or 4. wherein R-C-R represents an aliphatic hydrocarbon group COMPONENTB (FIXATIVE) CONTAINING OH GROUPS containing one to 12 carbon atoms, R' is hydrogen or a lower Component B in this category may be any of the aromatic, alkyl radical. 5 aliphatic, or heterocyclic compounds containing at least two it is also evident that the sulphur analogues of the hydroxy groups. The compounds may be hydrocarbon polyols bischloroformates may be used and such are included within or may contain noninterfering (nonfunctional) radicals such the spirit of the invention. Thus, instead of using the com as ether groups, thioether groups, sulphone groups, etc. Typi pounds containing haloformate groups, one may use any of 20 cal compounds in this category are listed below by way of ill the compounds containing the sulphur analogues of these lustration but not limitation: ethylene glycol, diethylene groups, for example, the compounds containing two or more glycol, 2,2-dimethyl propane-1,3-diol, propane-1,3-diol, bu groups of the formula tane-l,4-diol, hexane-1,6-diol, octane-1,8-diol, decane-1,10 diol, dodecane-1,12-diol, butane-1,2-diol, hexane-1,2-diol, 1 25 O-methylglycerol, 2-O-methylglycerol, cyclohexane-1,4-diol, hydroquinone, resorcinol, catechol, bis(parahydroxyphenyl) methane, 1,2-bis(parahydroxyphenyl) ethane, 2,2- wherein one Z is sulphur and the other is oxygen or wherein bis(parahydroxyphenyl) propane, 2,2-bis(parahydroxyphen both Z's are sulphur. The symbol X in the above formula yl) butane, 4,4'-dihydroxybenzophenone, naphthalene-1,5- stands for a halogen. 30 diol, biphenyl-4,4'-diol, 2,2-bis(3-methyl-4-hydroxyphenyl) COMPONENTB (FIXATIVE) CONTAINING NHCOX propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl) propane, 2,2- GROUPS bis(4-hydroxy-dibromophenyl) propane, glycerol, diglycerol, Aromatic, aliphatic, or heterocyclic compounds containing hexanetriol, pentaerythritol, etc. Moreover, it is within the at least two carbamyl halide (-NHCOX) groups. The com 35 spirit of the invention to utilize the sulphur analogues of the pounds may be hydrocarbon carbamyl halides or may contain diols. Thus, for example, instead of using the compounds con noninterfering (nonfunctional) groups such as ether, taining two hydroxy groups one can use the analogues con thioether, sulphone, etc., groups. Typical compounds in this taining either (a) two -SH groups or (b) one -SH group and category are given below by way of illustration and not by way one -OH group. of limitation: ethylene dicarbamyl chloride, trimethylene 40 Among the preferred compounds are the aliphatic diols, for dicarbamyl chloride, tetramethylene dicarbamyl chloride, example, those of the type: hexamethylene dicarbamyl chloride, octamethylene dicar HO-(CH)-OH bamyl chloride, 2-methylpropane-1,2-dicarbamyl chloride, wherein in has a value from 2 to 12. Another preferred catego 2,6-dimethyloctane-2,7-dicarbamyl chloride, cyclohexane ry of aliphatic compounds are the polyethylene glycols, i.e.: 1,4-dicarbamyl chloride, diethyl ether-2,2'-dicarbamyl 45 HO-CH-CH-O-CH-CH-O-CH-CH-OH chloride, diethyl thioether-2,2'-dicarbamyl chloride, wherein n has a value from zero to 10. A preferred category of piperazine dicarbamyl chloride, o-, m-, and p-phenylene aromatic diols are the bisphenols, that is, compounds of the dicarbamyl chloride, xylylene dicarbamyl chloride, and their type: sulphur analogues, i.e., the corresponding dithiocarbamyl chlorides. If desired, mixtures of different di- or tricarbamyl 50 halides may be used. It is generally preferred to use com f pounds of the type Ho----OH XCONH-(CH)-NHCOX R. R. R. wherein X is F, Cl, Br, or I and n has a value of 2 to i2. 55 wherein R-C-R represents an aliphatic hydrocarbon group COMPONENTB (FIXATIVE) CONTAINING NH, OR NH containing one to 12 carbon atoms, and R' represents GROUPS hydrogen or a lower alkyl radical. In this category especially preferred compounds are 2,2-bis(parahydroxyphenyl) Component B in this category may be any of the aromatic, propane, often designated as bisphenol-A, 2,2-bis(3-methyl-4- aliphatic, or heterocyclic compounds containing at least two 60 hydroxyphenyl) propane; 2,2-bis(3-isopropyl-4-hydroxyphen amine (-NH) or imine (-NH-) groups. The compounds yl) propane; and brominated derivatives of bisphenol A, such may be hydrocarbon amines or imines or may contain nonin as 2,2-bis(4-hydroxy-dibromophenyl) propane. terfering (nonfunctional) groups such as ether groups, The hydroxy compounds are employed as such in the phase thioether groups, sulphone groups, fluorine groups, etc. Typi boundary-limited cross-linking or in the form of their alkali cal compounds in this category are listed below by way of ill 65 lustration but not limitation: ethylene diamine, trimethylene metal salts, that is, as alcoholates or phenolates, depending on diamine, tetramethylene diamine, hexamethylene diamine, whether the polyols are aliphatic or aromatic. octamethylene diamine, decamethylene diamine, N,N'- COMPONENTB (FIXATIVE) CONTAINING -NCO dimethyl-1,3-propanediamine, 1,2-diamino-2-methylpropane, GROUPS 2,7-diamino-2,6-dimethyloctane, N,N'-dimethyl-1,6-hex 70 anediamine, 1,4-diamino cyclohexane, i,4-bis-(aminomethy) Component B in this category may be any of the aliphatic, cyclohexane, 2,2'-diaminodiethyl ether, 2,2'-diaminodiethyl aromatic, or heterocyclic compounds containing at least two sulphide, bis-(4-aminocyclohexyl) methane, N,N'-dimethyl isocyanate (-NCO) groups. The compounds may be 2,2,3,3,4,4-hexafluoropentane-1,5-diamine, ortho-, meta-, or hydrocarbon isocyanates or may contain nominterfering (non para-phenylene diamine, benzidine, xylylene diamine, m 75 functional) radicals such as ether groups, thioether groups, 3,632,391 17 8 sulphone groups, tertiary amine groups, etc. Typical examples that no after treatment (curing) is required. The boundary may of compounds in this category are listed below merely by way be between different types of phases-solid, liquid, or gase of illustration and not limitation: ethylene diisocyanate, ous-with the proviso that at least one phase must be fluid, propylene diisocyanate, butylene diisocyanate, trimethylene i.e., liquid or gaseous. Thus, the component A may be present diisocyanate, tetramethylene diisocyanate, hexamethylene as a solid phase (e.g., applied in solution, followed by evapora diisocyanate, octamethylene diisocyanate, decamethylene tion of solvent) and component B as a liquid or gas phase. diisocyanate, cyclohexylene diisocyanate, bis(2-iso: Where component A is applied as a liquid phase, component cyanatoethyl) ether, bis(2-isocyanatoethyl) ether of ethylene B is applied as a solid, liquid, or gas phase. Generally, a system glycol, o-phenylene diioscyanate, m-phenylene diisocyanate, of liquid-liquid phases is preferred, and particularly wherein p-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene 10 the phases are mutually insoluble whereby to preserve the 2,6-diisocyanate, 3,3'-bitolylene-4,4'-diisocyanate, diphenyl boundary between the phases. Thus in a preferred embodi ether-4,4'-diisocyanate, 3,5,3',5'-bixylylene-4,4'-diiso ment of the invention, the selected components A and B are cyanate, diphenylmethane-4,4'-diisocyanate, biphenylene formed into separate solutions, using solvents which are sub diisocyanate, 3,3'-dimethoxy-biphenylene-4,4'-diisocyanate, stantially mutually immiscible. Thus, for example, component naphthalene diisocyanates, polymethyl polyphenyl iso 15 B is dissolved in water and component A is dissolved in cyanates, and reaction products of polyhydric alcohols with benzene, carbon tetrachloride, toluene, xylene, ethylene excess diisocyanate, for example, compounds of the formulas: dichloride, chloroform, hexane, octane, petroleum ether or other petroleum distillate, or any other inert, water-immisci ble solvent. The two solutions are then applied to the fibrous 20 substrate serially; that is, the substrate is treated first with one solution, then with the other. The order of applying the solu GH-Z tions is not critical. Generally, the solution of component B is C (CH-O C-NE-qi-NC O) and GH-Z applied first and the solution of component A is applied next. 25 However, the reverse order gives good results and it is within CI CH-Z the ambit of the invention to apply the solutions in either sequence. The solutions may be applied to the fibrous material in any way as long as they are applied serially. A preferred method wherein Z stands for the radical involves immersing the material in one solution, removing ex cess liquid as by the use of squeeze rolls, immersing the material in the second solution, and again removing excess e liquid. To remove unreacted materials, solvents, etc., the -O C-NH-Hi-Nc O material may then be washed and/or rinsed. Then, after dry CH, 35 ing, it is ready for use or sale. Conventional apparatus consist ing of tanks, padding rolls, squeeze rolls, and the like are It is also evident that the sulphur analogues of these com generally used in applying the respective solutions. The pounds may be used and such are included within the spirit of amount of each component applied to the fibrous material the invention. Thus for example, instead of using the com may be varied by altering the residence time in the solutions, pounds containing two -NCO groups one may use their 40 the pressure exerted by the squeeze rolls, and by varying the analogues containing either two -NCS groups or one -NCO concentration of the active ingredients in the respective solu group and one -NCS group. tions. To decrease carryover of the solvent from the first treat Among the preferred compounds are the aliphatic diiso ing solution to the second solution, the fibrous substrate after cyanates, for example, those of the type its immersion in the first solution may be subjected to drying 45 conditions such as exposure to a current of warm air to wherein n has a value from 2 to 12. Other preferred com evaporate at least part of the solvent and hence concentrate pounds are the toluene diisocyanates, xylylene diisocyanates, the solution carried by the fibers. and diphenylmethane-4,4'-diisocyanate which may also be As noted above, a critical factor in the preferred form of the termed methylene-bis(p-phenylisocyanate). invention is that the complementary agents-component A 50 and component B-are serially applied to the textile dispersed COMPONENT B (FIXATIVE) CONTAINING in solvents which are substantially mutually immiscible. The ANHYDRIDE ORMIDE GROUPS nature of the solvents is of no consequence as long as they are essentially inert and possess the above-stated property of sub Component B in this category may be any of the aliphatic, stantial immiscibility. Usually, volatile solvents are preferred aromatic, or heterocyclic compounds containing at least two 55 as they may be removed from the treated textile by evapora anyhydride or imide groups. The compounds may be tion. However, nonvolatile solvents can be used, in which case hydrocarbon anhydrides or imides or may contain noninter they may be removed from the product by extraction with fering (nonfunctional) radicals such as ether groups, thioether suitable volatile solvents therefor or washed out with soap and groups, sulphone groups, tertiary amine groups, etc. Typical water or detergent and water formulations. In some cases illustrative examples in this category are: 334,4'- 60 component A is soluble in water and may thus be applied to benzophenone tetracarboxylic dianhydride or diimide, the textile in aqueous solution. In such case the solvent for cyclopentanetetracarboxylic dianhydride or diimide, component B may be any inert, essentially water-immiscible cyclohexanetetracarboxylic dianhydride or diimide, pyromel organic solvent. Typical illustrative examples thereof are litic dianhydride or diimide, etc. 65 benzene, toluene, xylene, carbon tetrachloride, ethylene dichloride, chloroform, hexane, octane, petroleum ether or PROCEDURE other volatile petroleum fraction. Usually, however, com As mentioned above, a feature of the present invention is ponent A, because of its high molecular weight, is insoluble in that cross-linking of the preformed polymer takes place under water and is preferably applied in solution in a substantially phase boundary-limited reaction conditions. This means that 70 water-immiscible organic solvent, such as any of those listed component A and component B must be present on the above. In such case, component B would be applied in aque fibrous substrate in separate phases so that the cross-linking ous solution. It is, of course, obvious that many of the contem reaction will take place at the boundary between the phases. plated highly reactive groups will react with water (e.g., iso This is, of course, a very desirable situation as under such con cyanate, carbonyl halide, sulphonyl halide, carbamyl halide, ditions the cross-linking takes place almost instantaneously so 75 haloformate, anhydride, and imide groups) and hence com 3,632,391 9 2 ponents which contain these are not normally applied in aque polyhydric alcohols, with partial esters of fatty acids and ous solutions. polyhydric alcohols or with alkyl phenols, etc. Typical of such Although one of the complementary solutions generally has agents are a polyoxyethylene stearate containing about 20 ox water as a solvent, such a system is not essential and one may yethylene groups per mole, a polyoxyethylene ether or sor utilize a system of two essentially immiscible organic solvents, 5 bitan monolaurate containing about 16 oxyethylene groups component A being dispersed in one solvent and component B per mole, a distearate of polyoxyethylene ether of sorbitol in the other. As an example, component A may be dispersed in containing about 40 oxyethylene groups per mole, iso-octyl 2-bromoethyl acetate and component B dispersed in benzene. phenyl ether of polyethylene glycol, etc. Generally, only a Another example involves using formamide, dimethylforma small proportion of surface-active agent is used, on the order mide, or diethylformamide as the solvent for component A O of 0.05 to 0.5 percent, based on the weight of the solution. In and using n-hexyl ether as the solvent for component B. A addition to, or in place of the surface-active agent, a supple further example involves a system of adiponitrile as the sol mentary solvent may be added to the primary solvent (water) vent for component A and ethyl ether as the solvent for com in quantity sufficient to disperse the active reactant. For such ponent B. Examples of other pairs of solvents which are sub purpose one may employ acetone, or other inert, volatile sol stantially immiscible with one another and which may be used 15 vent, particularly one that is at least partially miscible with for preparing the solutions of the respective reactants are 2 water. It is evident that the solutions of components A and B bromoethyl acetate and n-hexyl ether, ethylene glycol need not necessarily be true solutions, they may be colloidal diacetate and n-hexyl ether, adiponitrile and n-butyl ether, solutions, emulsions, or suspensions, all these being con adiponitrile and carbon tetrachloride, benzonitrile and forma sidered as solutions for the purposes of the present invention. mide, n-butyl ether and formamide, di-N-propyl aniline and Ordinarily, the treatment of the fibrous substrate with the formamide, isoamyl sulphide and formamide, benzene and solutions of the complementary agents is carried out at room formamide, butyl acetate and formamide, benzene and temperature as at such temperature the polymerization takes nitromethane, n-butyl ether and nitromethane, carbon place very rapidly, that is, in a matter of a minute or less. If, tetrachloride and formamide, dimethyl aniline and forma 25 however, a higher rate of polymerization is desired-as in con mide, ethylbenzoate and formamide. tinuous operation on long lengths of cloth-the second solu The concentration of active materials (component A and tion may be kept hot, for example, at a temperature of 50 to component B) in the respective solutions is not critical and 150° C. Also, where the agents used include a polyol as such may be varied widely. Generally, it is preferred that each of (in contrast to the alkali salt thereof) it is preferable to heat the pair of solutions contains about from 0.5 to 20 percent of 30 the second solution as the cross-linking rates with the polyols the respective active component. In applying the process of are generally unsatisfactory at room temperature. the invention, enough of the respective solutions are applied As has been explained above, in the preferred modification to the fibrous substrate to provide a cross-linked polymer on of the invention the solutions of components A and B are seri the fibers in the amount desired. In treating some substrates ally applied to the fibrous material in the form of mutually im such as textiles it is desired to limit the amount of cross-linked 35 miscible solutions to provide a liquid-liquid interface between polymer to about 1 to 10 percent of the weight of the textile, the solutions as they are serially laid onto the fibers. In a less whereby to achieve the desired modification-e.g., shrink preferred modification of the invention, a system is used proofing-without damaging the hand of the textile. W which utilizes a solid-liquid interface. Such a system is It is often desirable to add reaction promoters or catalysts to established in the following way: The fibrous material is first either of the solutions of components A or B in order to 40 impregnated with a solution of one of the complementary enhance reaction between the active agents. For example, in agents-for example, component A-dispersed in an inert, cases where the system involves reaction between (1) amine volatile solvent. The substrate is then subjected to drying as by or hydroxy groups and (2) carbonyl chloride, sulphonyl exposing it to a current of hot air. The fibers which are now chloride, carbamyl chloride, or chloroformate groups, it is covered with a deposit of the first component in a solid state, desirable to add to the solution of the component containing 45 are then impregnated with the complementary agent-com the amine or hydroxy groups a sufficient amount of alkaline ponent B, in this case, dispersed in an inert, preferably volatile material to take up the HCl formed in the reaction. For such solvent. in this way the fibers are layered with a superposed purpose one may use a tertiary amine such as pyridine, system of solid component A and a solution of component B. dimethyl aniline, or quinoline or an alkali-metal hydroxide, or, Under these conditions cross-linking takes place rapidly, more preferably, an alkaline material with buffering capacity 50 forming the three-dimensional polymer in situ on the fibers. In such as sodium carbonate, sodium bicarbonate, trisodium this system it is not essential that the respective solvents be im phosphate, borax, sodium metasilicate, etc. Another plan miscible. Thus, for example, component A may be applied in which may be used in instances where one component con water solution and component B in a water-miscible solvent tains amino groups, involves supplying said component in ex such as dioxane or acetone. This and other phases not involv cess so that it will act both as a reagent and as an HC-accep ing liquid-liquid boundary cross-linking are described in some tor. The reaction of components A and B may also be cata of the examples below, e.g., example I, runs 2 and 4. lyzed by addition of such agents as tributyl tin chloride, stan In a preferred embodiment, the invention is applied to wool nous tartrate, ferric chloride, titanium tetrachloride, boron as the fibrous substrate whereby to attain such desirable trifluoride-diethyl ether complex, or tin salts of fat acids such 60 results as increasing the resistance of the textile to shrinking as tin laurate, myristrate, etc. Such catalysts are particularly and felting when subjected to washing operations, increasing useful to promote reaction between components containing the resistance of the textile to becoming soiled in use, enhanc hydroxy groups and those containing isocyanate, acid ing resistance to bleaches and to light, decreasing the ten chloride, or chloroformate groups. dency of the textile to becoming creased or wrinkled during Where one of the solutions of the reactants contains water 65 wear or during washing and drying operations, i.e., to provide as the solvent, it is often desirable to incorporate a minor pro it with “easy-care" properties so that ironing after laundering portion of a surface-active agent to aid in dispersing the reac is largely eliminated. Moreover, these desirable effects are at tant and to assist in penetration of the solution into the textile. tained without impairing such desirable properties as tensile For this purpose one may use such agents as sodium alkyl strength, abrasion resistance, elasticity, porosity, and hand of (CCs) sulphates, the sodium alkane (Cs-Cs) sulphonates, 70 the material so that textiles modified in accordance with the the sodium alkyl (Cs-Cao) benzene sulphonates, esters of invention may be used in fabricating garments of all kinds. sulphosuccinic acid such as sodium dioctylsulphosuccinate, The invention may be applied to wool in any physical form, for and soaps, typically sodium salts of fat acids. Emulsifying example, bulk fibers, top, sliver, roving, webbing, yarn, felt, agents of the nonionic type are suitable, for example, the reac woven textiles, knitted textiles, completed garments or gar tion products of ethylene oxide with fatty acids, with 75 ment parts, and other fabricated forms such as carpets, rugs, 3,632,391 2. 22 blankets, cords, tapes, etc. As noted hereinabove, the per polymers for use as component A are stability to oxidation and manence of modification obtained in accordance with the in light, good film-forming ability, availability of a wide spectrum vention is primarily based on converting the preformed of types and individual species, and the fact that many are polymer into an insoluble, cross-linked (three-dimensional) 3 relatively inexpensive compared to other classes of polymers. dimensional) structure. However, it is evident that in treating In the preferred practice in accordance with this embodi wool in accordance with the invention, one may additionally ment of the invention, component A is an addition polymer obtain a chemical combination of the polymer with the wool containing (as the highly reactive groups) carbonyl halide, in such cases where the preformed polymer and/or the fixative sulphonyl halide, haloformate, isocyanate, carbamyl halide, or contains groups capable of reacting with reactive sites on the anhydride groups and is applied to the fibrous substrate in the 10 form of a solution in an inert, essentially water-immiscible sol wool molecules. Since such reactive sites are primarily of an vent. The complementary fixative (component B) is ac amine or hydroxy nature, it is believed that chemical combina cordingly applied as an aqueous solution and contains hydroxy tion (grafting) occurs in such instances where the agents ap groups, or, more preferably, amine or imine groups as the plied (components A or B) contain such reactive groups as highly reactive groups complementary to those on component carbonyl halide, haloformate, sulphonyl halide, carbamyl ha 15 lide, isocyanate, etc. A. Thus in operating in the sphere of the preferred modifica Although the invention is of particular advantage in its ap tion of this embodiment, component B may be chosen from plication to wool, this is by no means the only type of fiber any of the types exemplified above in the section entitled "- which comes into the ambit of the invention. Generically, the Component B (Fixative) Containing NH or NH Groups." invention is applicable to the treatment of any type of fibrous 20 Coming under special consideration is the use, as com material, for example, animal hides and leather, silk, animal ponent A, of copolymers of (a) methacryloyl chloride or hair, mohair, cotton; sisal; hemp, jute, ramie, flax, wood; acryloyl chloride (to provide free COCl groups) with (b) paper, synthetic cellulosic fibers such as viscose, cellulose other polymerizable unsaturated monomers free from highly acetate, cellulose acetate-butyrate, saponified cellulose reactive groups, typically such monomers as olefines, esters of 25 acrylic or methacrylic acid, vinyl esters and ethers, vinyl acetate, cupraammonium rayons, ethyl cellulose; polyvinyl al chloride, etc. cohol-protein fibers; algin and pectin fibers; glass fibers; Especially useful are the copolymers containing units asbestos, organic noncellulosic fibers such as polyethylene derived from (1) acryloyl or methacryloyl chloride and (2) terephthalate, polyacrylonitrile, polyethylene, polypropylene, from an olefine such as ethylene, propylene, isobutylene, or polyvinyl chloride, polyvinylidene chloride, nylon, polyu butadiene. Usually, a third type of unit is included to decrease rethanes; regenerated protein fibers such as those prepared 30 crystallinity and to increase solubility. For these purposes, the from casein, soybeans, peanut protein, Zein, gluten, egg albu copolymer may contain units derived from (3) esters of acryl min, collagen, or keratins such as animal hoof or horn; mix ic or methacyrlic acid, vinyl esters of fatty acids, vinyl ethers, tures of any of the above such as textiles containing cellulosic vinyl chloride, or the like. These copolymers may be directly and noncellulosic fibers, blends of synthetic fibers or cotton 35 prepared from the monomers. More usually, acrylic or with wool, etc. The invention may be applied to such fibrous methacrylic acid is copolymerized with the olefine and the materials in any state such as bulk fibers, staple fibers, slivers, third type of monomer and the product is treated to convert yarns, woven or knitted textiles, felts, fabricated articles such the free acid groups to carbonyl chloride groups. Thus as garments and garment parts. The application of the inven although not made directly, the final product can still be con tion may be for the purpose of obtaining any of a wide variety 40 sidered as a copolymer of acryloyl or methacryloyl chloride of functional or decorative effects such as sizing, increasing with the olefine and the third type of monomer. A typical for gloss or transparency, increasing water-, oil-, or soil-repellen mulation for this type of copolymer would be, for example, 1 cy, increasing adhesion or bonding characteristics of the sub to 10 mole percent of methacryloyl chloride, 5 to 10 mole per strates with rubber or other elastomers, imparting softness or cent of vinyl acetate, or the like, and the remainder (to 100 lubricity, imparting shrinkage resistance, decreasing tendency 45 mole percent) of the olefine. to wrinkle, crease and pill during wear or during washing and This embodiment l of the invention is further demonstrated drying operations, etc. In cases where the fibrous material is a by the following illustrative examples: hydrogen-donor (that is, where its molecules contain active hydrogen as in amine or hydroxy groups), it would be ex EXAMPLES pected that during application of the process of the invention, 50 Accelerotor Shrinkage Test: This test for shrinkage was a chemical combination of the polymer to the fiber molecules conducted in the following way: The wool samples were milled will take place, particularly where either the preformed at 1,700 r.p.m. for 2 minutes at 40-42 C. in an accelerotor polymer or the fixative contains such highly reactive groups as with 0.5 percent sodium oleate solution, using a liquor-to carbonyl halide, sulphonyl halide, carbamyl halide, halofor wool ratio of 50 to 1. After this washing operation the samples mate, or isocyanate. Typical examples of hydrogen donor 55 were measured to determine their area and the shrinkage was fibers (in addition to wool) are the natural cellulosic fibers, calculated from the original area. The accelerotor is described viscose rayons, saponified cellulose acetate fibers, etc. in the American Dyestuff Reporter, Vol. 45, p. 685, Sept. 10, Having now described the types of compounds which may 1956. The two-minute wash in this device is equal to about 15 be used as components A and B and how they are applied to home launderings. fibrous materials, we will next explain the various preferred 60 Washing Machine Shrinkage Test: The wool samples were embodiments of the invention. In the procedure of the inven washed in a reversing agitator-type household washing tion, the type of preformed polymer employed is the deter machine, using a 3-lb. load, a water temperature of 105 F., minative factor because of the large molecular weight thereof and a low-sudsing detergent in a concentration of 0.1 percent in comparison to that of the fixative or the cross-linking units 65 in the wash liquor. The wash cycle itself was for 75 minutes, derived therefrom. Accordingly, the various subgeneric em followed by the usual rinses and spin drying. In most cases this bodiments of the invention are based on the type of preformed washing program was repeated several times. The damp polymer, i.e., component A. material was then tumble-dried in a household-type clothes dryer. The samples were then measured to determine their EMBODIMENT 1 70 length and width and the shrinkage calculated from the in this preferred embodiment of the invention, component original dimensions. A is an addition polymer. Numerous examples thereof are Oil Repellency Test: The 3M oil repellency test described listed hercinabove in the sections entitled "Component A by Grajeck and Petersen, Textile Research Journal, 32, pp. (Addition Polymers)" and "Component A (Converted Addi 320-331, 1962. Ratings are from 0 to 150, with the higher tion Polymers)." Among the special advantages of addition 75 values signifying the greater resistance to oil penetration.

3,632,391 23 24 Water Repellency: AATC spray test, method 22-1952. (Untreated) Ratings are from 0 to 100 with the higher values signifying greater resistance to water penetration. The products of runs t, 2, and 3 were tested for their coeffi EXAMPLE 5 cient of friction by drawing individual fibers over a glass rod in 1. Solution A: Component A was a terpolymer of ethylene the direction against the scales. In this test a smaller value in (80 percent), vinyl acetate (15 percent), and methacryloyl dicates a smoother fiber surface. The results are given below: chloride (5 percent). Its molecular weight was about 50,000 Wt, resin Friction coefficient and it contained about 40-50 carbonyl chloride groups per 10 Run on fabric, (against scales) polymer molecule. Solutions were made of this terpolymer in -- % methyl chloroform at concentrations of 3 percent and 1.5 per 1 3. 0.152. cent. 2 0.74 2. Solution B: 0.5 percent hexamethylene diamine (com 3 0.5 0.24 ponent B), 1 percent sodium carbonate, and 0.05 percent Control O 0.30 wetting agent (isooctylphenyl ether of polyethylene glycol) in 15 (Untreated water. 3. A sample of wool cloth was immersed in one solution at EXAMPLE room temperature for about 30 seconds, run through squeeze Solution A: The same terpolymer as in example I was dis rolls to remove excess liquid, immersed for about 30 seconds solved at a concentration of 1.5 percent in a petroleum solvent in the complementary solution at room temperature, run (a commercial hydrocarbon mixture having the following through squeeze rolls to remove excess liquid, rinsed in water, characteristics: 96 percent aromatics, 3 percent naphthenes, 1 and dried in air at room temperature. percent paraffins, Sp.G. 0.87, boiling range 314-362 F.). 4. The sequence of treatment with the respective solutions Solution B: Contained 0.5 percent of a specific diamine (as and the results of shrinkage tests on the products are tabulated 25 given below), 1 percent sodium carbonate, and 0.05 percent below: of wetting agent (isooctylphenyl ether of polyethylene glycol) Order Conc. of Area shrinkage in aqueous solution. The various diamines used are listed Ruin solutions terpolymer Accelerotor), below: in Sol. A,% % 30 Diannine Abbreviation B-A 3 8.8 2 B-A 3 4.9 Ethylene diamine EDA 3 B-A 5 6.9 1,3-Diaminopropane DPA 4 B-A 5 4.9 Propylene diamine PDA 5 A-B. 3 3.0 35 Hexamethylene diamine HMDA Control --- 29.0 Piperazine Pip (Untreated wool) in these cases, the cloth, after application of solution B, was air dried prior to im mersion in solution A. Wool cloth was treated with the solutions as in example I, 40 part 3. In all cases the sequence of treatment was B-A. The results are given below: EXAMPLE II Percent area shrinkage, cumulative" after Solution A: The same terpolymer as in example I was dis Component ------solved in methyl chloroform at concentrations of 3 percent, 1 45 Run B used Wash Wash 2 Wash 3 Wash 4 percent, and 0.5 percent. ------EDA 0.9 i. 2.0 1.2 Solution B: 0.5 percent ethylene diamine (component B), 0.8 2.5 3, 4 3. .5 1.9 2,8 2,5 percent sodium carbonate, and 0.05 percent wetting agent 1.0 0.1 0. 0.5 (isooctylphenyl ether of polyethylene glycol) in water. 2.8 3, 1 15.5 21.9 Wool cloth was treated with the solutions as in example I, 9. 30.5 35.4 3.5 part 3. " Successive 75-minute washes in automatic hone washing machite, The sequence of treatment with the respective solutions and as described above. the results obtained are as follows: EXAMPLE IV Percent area shrinkage, cumula 55 Conc. of tive' after Solution A: The same terpolymer as in example I was dis Order of terpolymer ------applying in Sol. A., Wash Wash Wash Wash solved in methyl chloroform (or Stoddard solvent) at a con Run solutions percent - 2 3 4 centration of 1.5 percent. 1------A-B 3. 0, 2 0, 5 0.3 0.5 Solution B: Same as in example III. 2------A-B 0.2 0.9 0.4 0. Wool cloth was treated with the solutions as in example I, 3------A-B 0.5 1.0 3.5 4.7 9.4 60 4------B-A 3 0.3 1.5 0.5 0.5 part 3. In all cases, the sequence of treatment was B-A. The Control------19. 30.5 35.5 3.5 results are given below: * Successive 75-minute washes in automatic home washing machine, agitator type. See text above for details of wash method. Percent area shrinkage, ctimu 65 Com- lative "after The products of runs 1, 2, and 3 were subjected to tests for Solvent for con- ponent ------abrasion resistance, using a Stoll flex abrader, Run. ponent. A Blised Wash Wash2 Wash 3 Wash 4 ASTM:D1175-5ST. The results are as follows: 1------Methyl chloro- EDA i.3 2.0 3.0 1.3 form. 2------do------DPA 0.7 2.5 3.2 3.5 Wit. resin Abrasive resistance, 8------do------PDA 1.0 1.9 2.5 2.2 Run on fabric, cycles to break 70 ------do------HMDA 0.2 0.5 0.2 0. Warp Fill ------do------Pip 1.2 1.5 2.7 2.2 6--- Stoddard solvent. EDA ? 0. 0 0.7 7------do------HMDA 0.8 0.6 0.3 0.7 3. 80 77 Control------8.8 30.5 36.4 39.5 2 t 76 969 * Successive 75-minute washes in automatic hone washing machine, 3 0.5 550 588 75 Control O 457 S47 as described above.

H 3,632,391 25 EXAMPLEV Percent area shrink Weight of polymer age cumulative" A solution of 95 ml. styrene, 5 ml. methacryloyl chloride, on fabric, percent after Conc. of ------and 1,000 ml. of benzene, containing 0.2 g. azo-bis-isobu copolymer Before After tyronitrile, was swept with dry nitrogen for 30 minutes and in Sol. A. extract extrac then heated to 70-80 in a closed vessel for 8 hours. The Procedure percent tion tion Washi Wasl resulting solution of the styrene-methacryloyl chloride In accordance with invention.------5 2.2 .5 10 3.0 copolymer (containing more than 3 carbonyl chloride groups In accordance with per molecule) was used to treat test swatches of wool as in ex invention------2.5 1, 5 (2) 33.4 39.0 Control (No treat ample I, part 3. Various aqueous solutions of diamines were O ment with Sol. used in the first treatment step; these diamine solutions con B)------5 5.2 0.2 7.0 1 13, O tained 0.5 percent of the specified diamine, 1.0 percent sodi Blank ------0.0 20, O um carbonate, and 0.1 percent wetting agent. Abbreviations * Successive 75-minute washes in automatic home washing machine, as described above. for diamines are given in example III. 1 Shrinkage tested after extraction. 15 Not determined. Step 1 Step 2 % Area shrinkage, 3 Shrinkage tested before extraction. Accelerotor EXAMPLE VII

(Diamine Treatment of wool with a terpolymer containing styrene, used lauryl methacrylate and methacryloyl chloride, the terpolymer EDA Copolyner Soln. 6.3 containing three or more carbonyl chloride groups per HMDA Copolymer Soln. 5.4 molecule. DPA Copolymer Soln. 19.0 PdA Copolymer Soln. 8. The terpolymer was prepared, using the following recipe: Pip Copolymer Soln. 19.9 52 ml. styrene Control 300 30 ml. lauryl methacrylate (Untreated) 25 10 ml. methacryloyl chloride 900 ml. benzene 0.2 g. azo-bis-isobutyronitrile The system was swept free of air by sweeping with dry EXAMPLE VI nitrogen and was kept under a nitrogen atmosphere during 10 30 hours of heating in a closed vessel at 70-80°C. The resulting A copolymer of methyl methacrylate and methacryloyl terpolymer solution was used to treat wool swatches: The test chloride (containing over three carbonyl chloride groups per swatches were first dipped in a 0.5 percent aqueous solution of copolymer molecule) was prepared as follows: 95 ml. of a diamine, passed through a squeeze roll, then immersed in the methyl methacrylate (redistd.) and 5 ml. of methacryloyl 35 terpolymer solution, again passed through the squeeze roll, chloride were placed in 500 ml. of dry benzene. The system and finally given a light wash in 0.1 percent detergent solution was flushed with dry nitrogen, 0.1 g. azo-bis-isobutyronitrile and dried at room temperature. The following results were ob added, and heated at 70-80 C. for 6 hours while held in a tained when the swatches were washed in an accelerated closed vessel. shrinkage test, using the accelerotor: The resulting copolymer solution was used to treat test 40 swatches of wool (14 inch by 14 inch): The test piece was first Step it Step 2 Area shrinkage, immersed in a solution, at room temperature, of 0.5 percent HMDA Terpolymer soln. 2.6 ethylene diamine in HO (containing 1.0 percent sodium car EDA Terpolymer solin. 50 bonate and 0.1 percent wetting agent), then passed through Control 30.0 squeeze rolls to give a wet pickup of about 60 percent. The 45 (Untreated) swatch was then immersed in the copolymer solution, at room temperature, and again passed through the squeeze rolls, fol lowed by a light 15-minute wash in 0.1 percent detergent solu EXAMPLE X tion, and finally dried at room temperature. The treated material shrank only 12 percent in a 75-minute wash in home 50 1,1-Dihydroperfluorooctyl acrylate (9 moles), methacryloyl washing machine, compared to 22 percent shrinkage by an un chloride ( mole), and o,a'-azodiisobutyronitrile (about 5 g.) treated swatch. as a polymerization initiator were heated together at 78°C. for 3 to 4 hours in a closed vessel. The resulting copolymer con EXAMPLE VII taining three or more pendant -COCl groups per molecule 55 was a tacky, solid resin. Solution A: The above polymer was dissolved in 1,3- A copolymer of lauryl methacrylate and methacryloyl bis(trifluoromethyl) benzene at a concentration of 3 percent. chloride (in 9515 mole ratio) was prepared by a standard bulk Solution B: 2 percent hexamethylene diamine, 2 percent polymerization technique-i.e., heating in a closed vessel at 80 sodium carbonate, and 0.01 percent wetting agent (isooc for 5 hours in the presence of a minor proportion of a,o'- 60 tylphenyl ether of polyethylene glycol) in water. azodiisobutyronitrile as a polymerization initiator. The Wool cloth was treated with these solutions as in example I, copolymer contained three or more carbonyl chloride groups part 3, applying the solutions in the order B-A. In a control per molecule. run, impregnation in solution B was omitted. Increase in Solution A: The copolymer above was dissolved in toluene weight in both cases was 1 percent. The products were tested at a concentration of 5 percent and 2.5 percent. 65 for oil and water repellency as prepared and after extraction Solution B: 4 percent ethylene diamine, 7 percent sodium with benzotrifluoride for 6 hours in a Soxhlet extractor. The carbonate, and 0.01 percent wetting agent (isooctylphenyl results are given below: ether of polyethylene glycol) in water. Oil repellency Water repellency Wool cloth was treated with the above solutions as in exam 70 Before After Before After ple I, part 3, applying the solutions in the order B-A. In a con extrac- extrac- extrac- extra trol run, impregnation in solution B was omitted. rocedure tio tion tion tiol The products were tested for shrinkage and also for per li accordance with investion.-- O 1) () O manence of the copolymer deposit by extraction with benzene Control (No treatnleint with for 2A, hours in a Soxhlet extractor. The results are tabulated Sol. B) ...----- 120 ( 100 50-60 below: 75 Blank (Utreated O O 50-60 50-60 3,632,391 27 28 EXAMPLE X The product was extracted with acetone for 6 hours and it was found that the product retained 93 percent of the resin The chloroformate of ethylene glycol methacrylate deposit. GH, 9 g EXAMPLE XI CH=C-é-O-CH-CH-O&C Solution A: component A was chlorosulphonated polyethylene of number average molecular weight about was prepared in 95 percent overall yield by reaction of 30,000 and of the formula ethylene glycol monomethacrylate with excess phosgene. The chloroformate was purified by distillation, b.p. 85°C. at 3 mm. 10 The chloroformate was copolymerized with lauryl -(CH-CH, CH gh CH-CH2 on) CE methacrylate to produce a copolymer containing at least three V Cl soc J chloroformate groups per molecule, using the following technique: Lauryl methacrylate (15g.), 5g of the chloroformate, 100 15 wherein n is approximately 17 and x is approximately 12. lt ml. dry benzene, and 200 mg. a,a’-azodiisobutyronitrile were was dissolved in benzene at a concentration of 1.5 percent. heated in a closed vessel at 79°C. for 8 hours. Solution B: 0.5 percent of hexamethylene diamine (HM Solution A: The copolymer solution prepared as given DA) or ethylene diamine (EDA), 1 percent sodium car above. bonate, 0.05 percent of wetting agent (isooctylphenyl ether of Solution B: Three percent hexamethylene diamine and 0.01 polyethyleneglycol) in water. percent wetting agent (isooctylphenyl ether of polyethylene Wool cloth was treated with these solutions as in example I. glycol) in water. part 3, applying the solutions in the order B (room tempera Wool cloth was treated with the above solutions as in exam ture, immersion time 1 min.)-A (60° C., immersion time 2 ple I, part 3, applying the solutions in the order B-A. In a con min.). The results are given below: trol run, impregnation with solution B was omitted. 25 The products were tested for shrinkage before and after an Component B % Area shrinkage, cumulative * extraction with chloroform-20 hours in a Soxhlet extractor. Run used Wash Wash 2 Wash 3 Wash 4 The results are given below: HMDA 0.3 9 3.7 5.0 30 2 EDA 0.5 3.9 6.7 s Control - 9.1 30.5 35.4 39.5 Approx. Percent area shrink wt. of age, accelerator * Successive 75-minute washes in automatic home washing machine, as described resin on ----- above. fabric, Before After Procedure percent extraction extraction 35 In accordance with invention------15 2 5 Control (Notreatment with Sol. B)- 15 O 12.6 Blank (No treatment) 30 ------

EXAMPLE XIII 40 Wool cloth was immersed in a solution containing 10 per cent ethylene diamine in acetone. The cloth was squeezed to EXAMPLE X remove excess liquid and air-dried to remove the solvent. It Solution A: Component A was a 1/1 copolymer of methyl was then immersed in a 5 percent solution of the vinyl ether and maleic anhydride having a specific viscosity of chlorosulphonated polyethylene (as in example XIl) for 2 1.0 to 1.4 (as 1 percent solution in methyl-ethyl ketone at 25° 45 minutes, squeezed and air-dried. C.). The repeating unit of this copolymer had the structure A piece of the treated cloth and a control (untreated) piece were placed in 5 percent sodium hypochlorite solution in water and observed to ascertain dissolution time of each. The results are given beiow: gch, 50 -CH-CH-CH-CH Elapsed time Untreated cloth Treated cloth O-cC C-O min. (control) N /

55 0. Vigorous evolution No evidence of bubbles of attack It was dissolved in ethyl acetate at concentrations of 3, 1.5, 20 Mostly dissolved do. and 0.7 percent. 20 Completely dissolved Still essentially Solution B: 2 percent hexamethylene diamine, 3 percent whole; attack sodium carbonate, and 0.01 percent wetting agent (isooc at edges tylphenyl ether of polyethylene glycol) in water. 60 Wool cloth was treated with the above solutions as in exam ple I, part 3, using the sequence B-A. EXAMPLE XV Tests for permanency of the finish were conducted by mea suring loss in weight after extraction for 6 hours with acetone. A copolymer of methacryloxymethyl pentamethyldisiloxane The product retained 95 percent of the resin deposit in this 65 test. In a control test wherein treatment with solution B (the fixative) was omitted, the cloth retained only 24 percent of the ch, CH3 copolymer deposit. in other runs, wool cloth was immersed in an acetone solu CH-i-o-HCH-O-E-G-CH,CE: CH CE tion of the copolymer, squeezed to remove excess liquid, air 70 dried to evaporate the acetone, immersed in an aqueous solu tion of 4 percent hexamethylene diamine, 7 percent sodium and the chloroformate of monoethylene glycol methacrylate carbonate, and 0.01 percent wetting agent (isooctylphenyl ether of polyethylene glycol), then rinsed in water and air CH, O dried. 75 CH=C-C-O-CH-CH-O CO Cl 3,632,391 29 30 was prepared by heating the following ingredients in a closed Conc. of Percent area shrinkage, Compo- cumulative' after vessel at 75° C. for 10 hours: nent. A Wit. resin ------1.5 grams of the siloxane compound as above Order of in Sol. A Compo- on fabric, Wash Wasl Wasl 0.8 gram of the chloroformate compound as above treatment percent ment B percent 3 5 15 cc. dry toluene (diluent) B-A------3 TDI 2.3 O () () A-B- 4 TDI- 3.6 () ... O 2. () 0.1 gram aa’-azobisisobutyronitrile (polymerization initia A-B- TDI 1.0 () 1. () 1. () tor) A-B- 0.5 TDI 0.45 () 1. () 2.0 A-B- 0.25 T). 0.22 () 1. ) 1.5 The viscous syrup resulting was diluted with additional A-B- 3 SC------2.9 () 1. () 2. () toluene to 3 percent and 6 percent concentrations and used as B-A- - 3 SC 2.8 () ... () 2. () O A-B------2 SC------... 4 () 1. ) 3. () solution A. Control 10 Nole---- 9.6 3.0 13.5 20.0 Solution B was a 5 percent solution of hexamethylene (A only). diamine and about 0.01 percent nonionic wetting agent in Blank.------None ---do----- Nolle 9.0 26.0 33.4 Water. Successive 75-minute washes in automatic home wasling machine, Wool cloth was treated with the solutions as in example I, agitator type, as described above. part 3, using the sequence B-A. The results of tests on the 15 Several of the products as prepared above were subjected to products are given below: extraction with acetone for 3 hours in a Soxhlet extractor to test the permanence of the cross-linked resin deposits. Also, shrinkage tests were determined after such extraction. The Water repellency - Area shrinkage 20 results are tabulated below: After (Accelerotor, . Before After accel- after extraC Conc. of Wt. of resin on extrac extrac erotor tion), Compo- fabric, percent Area shrinkage Wit. resin on fabric, wash percent nent Ain (Accelerotor, percent tion tion" Order of Sol.A, Compo- Before After ex- after extrac 80 100 100 1.6 treatment percent nent B extraction traction tion), perceilt 80 100 100 16.3 3 TDI 2.3 1.7 0. Control (untreated).----- . 50 ------27.0 4 TDI---- 3.6 3.2 2.0 3 SC------2.9 2.3 2.0 *Extraction was with benzene, 3 hours l in a Soxhlet extractor 3 SC------2.8 2.2 2.0 10 None---- 9, 6 2, 6 10.0 None --do------27.0 EMBODIMENT 2 30 - EXAMPLE XVI In accordance with this embodiment of the invention, com ponent A is a polyalkylene imine. Typical examples of such Solution A: Aqueous solution of the polyethylene imine polymers are exemplified above in the section entitled "Com described in example XV (concentration given below) plus ponent A (Polyalkylene Imines).' A special feature of these 35 ca. 0.01 percent nonionic wetting agent. polymers is that they contain built-in highly reactive groups on Solution B: Acetone solution containing 4 percent pyromel the polymer backbone, namely, -NH-groups. In addition, litic dianhydride. they contain terminal NH groups. Another feature is that they Wool swatches were treated in the following manner: The are soluble in water even at very high molecular weights, e.g., swatches were wet-out in solution B, passed through a squeeze 10,000 and above. Accordingly, they may advantageously be 40 roll to obtain about a 90 percent wet pickup, and air-dried at applied to the fibrous material in the form of an aqueous solu room temperature for about 20 minutes to remove the tion. The fixative (component B) in such case is then acetone solvent. The dried swatches were then immersed in preferably applied as a solution in an inert, substantially solution A at room temperature for one minute, passed water-immiscible solvent. Component B is preferably chosen through a squeeze roll to 90 percent wet pickup, washed to to provide isocyanate radicals as the complementary, highly 45 remove unreacted materials, and air-dried. reactive groups. Other fixatives which provide excellent The various products were tested for permanence of the results are those containing carbonyl halide, haloformate, or resin deposit by extraction with acetone for 3 hours in a anhydride groups. Thus the preferred types of compounds for Soxhlet extractor. Shrinkage was also tested after extraction. use as the fixative may be selected from those exemplified The results are given below: above in the sections pertaining to component B of the types 50 Wt. of resin on fabric, containing NCO, COX, OCOX, or anhydride groups. percent Area shrinkage This embodiment 2 of the invention is further demonstrated (Accelerotor, after by the following illustrative examples: Conc. of Component A Before After extraction), in Sol. A extraction extraction percent 2.5 6 9,7 EXAMPLE XV 3.7 16 7.8 ------27.0 Component A was a polyethylene imine of molecular EXAMPLE XVII weight about 30,000-40,000. Basically, this polymer had the 60 Wool swatches were immersed in an aqueous solution con structure taining 3.3 percent of polyethylene imine (as described in ex ample XV) and passed through squeeze rolls to a 100 percent wet pickup. The swatches were air-dried at room temperature. CH-CH-NH sco-100 The cloth was placed in a cylinder wherein it was exposed to a l 65 current of nitrogen carrying vapors of toluene diisocyanate. Following this treatment, the wool was washed and air-dried. Solution A: Aqueous solution of the above polyethylene imine This product and a control, in which the exposure to (concentration as given below) plus ca. 0.01 percent nonionic toluene diisocyanate was omitted, were tested by extraction wetting agent. with acetone for 3 hours in a Soxhlet extractor. Shrinkage Solution B: Benzene solution containing 4 percent of 70 tests were also conducted before and after extraction. The toluene diisocyanate (TDI) or sebacoyl chloride (SC). results are tabulated below: Wool cloth was treated with the above solutions as Wt. of resin Area shrinkage described in example I, part 3. on fabric,% (Accelerotor), 2% The particulars of the treatment, amount of resin deposited Before After Before After on the fabric, and shrinkage tests are given below: 75 Procedure extraction extraction extraction extraction

3,632,391 3. 32 in accordance Wool cloth was treated with the solutions as in example I, with invention 3.4 .7 4.0 6.9 Control 3.3 18.0 26.0 part 3, using the sequence B-A. As a control, in one run the No application treatment with solution B was omitted. of Td) Tests were carried out to determine the shrinkage charac Blank - 27.0 - teristics of the treated samples and also their permanence to extraction (with benzene, 3 hours). The results are tabulated below: EMBODMENT 3 Wt. of resin Area shrinkage In accordance with this embodiment of the invention, com 10 on fabric, (Accelerotor), ponent A is a polyurethane, or, more accurately, a polyether Before After Before After (or polyester) containing internal urethane groups and free Procedure Extraction extraction extraction extraction isocyanate groups. Typical examples of such polymers are ex In accordance emplified above in the sections entitled "Component A with invention 33 2.3 0. O (Polyethers)' and “Component A (Polyesters)", wherein it is 15 in accordance with invention .6 d O n.d. explained that these polymers may be prepared by reacting a Control 8.0 0. 8.5 220) polyether (or polyester) containing hydroxy groups with an (No treatment excess of a diisocyanate. An advantageous feature of the with Sol. B) Bank -- 27 - polyurethanes is that when they are cross-linked in the phase 20 boundary-limited reaction, they are converted into urethane n.d. = not determined elastomers and as a result the treated textile material exhibits an especially soft and full hand. Ordinarily, the polyurethane will contain free isocyanate radicals as the highly reactive groups and since these are It was observed that the products in accordance with the in water-sensitive, the polymer is applied to the fibrous substrate 25 vention had a fulier, softer hand than the original (untreated) in the form of an inert, essentially water-immiscible solvent fabric. such as benzene, toluene, or the like. The fixative (component B) is then preferably applied as an aqueous solution. Com ponent B is preferably chosen to provide amine or imine radi EXAMPLE XIX cals as the complementary, highly reactive group. Typical ex 30 amples are given above in the section entitled "Component B (Fixative) Containing NH or NH groups.' Component A was a polyurethane prepared by reacting a In a variation of the basic procedure of this embodiment, polyether containing hydroxy groups with excess toluene one may apply-as component A-a polymer of the class of 35 diisocyanate to yield a polymer containing free isocyanate polyethers (or polyesters) containing free hydroxy groups. groups (average, more than 2 per molecule). Viscosity of the Typical examples of these are given in the above sections enti polyurethane was 1,600 centipoises at 40°C.,220 centipoises tled "Component A (Polyethers)' and "Component A at 75 C. and contained 3.2 to 3.6 percent free isocyanate. (Polyesters)'. In such case one would utilize as component B Solution A: 3 percent of the polyurethane in methyl a compound containing free isocyanate groups (such as those 40 chloroform. exemplified above in the section entitled “Component B (Fix Solution B: 0.5 percent hexamethylene diamine (or ative) Containing NCO Groups'). In such case the end result ethylene diamine), 0.1 percent wetting agent (isooctylphenyl of the phase boundary-limited reaction will be a cross-linked ether of polyethylene glycol) in water. polyurethane polymer. Wool cloth was treated with the solutions as described in ex This embodiment 3 of the invention is further illustrated 45 ample I, part 3, using the sequence B-A. Shrinkage tests of the below: products are given below: EXAMPLE XVII APPLICATION OF AN ISOCYANATE-CONTAINING % Area shrinkage, cumulative * POLYURETHANE TO WOOL 50 Diamine used Washi I Wash2 Wash 3 Wash 4 Poly(propylene oxide) glycol of an average molecular HMDA 1.5 0.2 2. 4.9 weight 2000 and a hydroxyl number of 56 was chain-extended EDA 1.3 0.4 8 3.3 and end-capped with 2,4-tolylenediisocyanate in the following Blank (Untreated) 19. 30S 35.5 39.5 manner: A dry, 3-neck, 500-ml. flask, fitted with stirrer, 55 dropping funnel, nitrogen inlet and thermometer was charged * in successive 75-minute washes in automatic home washing machine, as with 100 g (0.05 mole) poly(propylene oxide) glycol described above. (average molecular weight 2000) and this was heated with stirring under nitrogen to 75°C. Tolylene diisocyanate (17.4 g-0.1 mole) was then added slowly over a 15-20 minute 60 period via the dropping funnel. The mixture was stirred at EXAMPLE XX 75-80 C. for 3 hours. An infrared spectra of the viscous syrup showed no free -OH but did show the expected strong band at 4.4 microns (N=C=O) and a weak band at 5.8 microns Solution A: A polyoxypropylene triol (average molecular 65 weight 1,500; average hydroxyl No. 1 12) was dissolved in O acetone at various concentrations as given below: (-NHCO Solution B: 3 percent by volume of toluene diisocyanate in benzene. Wool cloth was treated as described in example I, part 3, , arising from chain coupling). The polymer was dissolved in 70 using the sequence A-B and the cloth was air-dried after dry toluene. Polymer concentrations of 9 and 2 percent were removal from solution A and prior to entering into solution B. used as solution A. The aqueous treating solution B contained The products, and a control sample in which the treatment 4 percent (by volume) of triethylenetetramine and ca. 0.01 with Solution B was omitted, were tested for shrinkage before percent of the wetting agent (isooctylphenyl ether of and after extraction with acetone for 3% hours in a Soxhlet ex polyethylene glycol). 75 tractor. The results are given below: 3,632,391 33 34 Area shrinkage Wool swatches were wet-out in solution A for various times percent (as given below), passed through a squeeze roll, and air-dried Conc. of poly- Wt. of ------oxypropylene resill on Before After at room temperature for one hour to remove solvent. The triol in Sol. fabric, extrac- extrac dried swatches were then dipped in solution B at room tem Procedure A, percent percent tion tiol 5 perature for one minute, passed through a squeeze roll, hand 4. 4. 4.0 7.0 washed and air-dried. Shrinkage tests on the products and a In accordance with 2 2 5.9 N.d invention.------7, 8 Nd control sample (whereon the treatment with solution B was 0.5 0.5 7.8 Nd omitted) were tested for shrinkage. The results are given Control (Treated with Sol. A only)------4. 4. 18. 23.4 below: Blank (Untreated)------27 ------10 Area NOTE.-N.d. = not determined. Wit. poly. Immersion shrinkage EMBODIMENT 4 amide in time in (Acceler Sol. A., Sol. A, otor), per In accordance with this embodiment of the invention, com Rul Procedure percent (sec.) cent 15 ponent A is a polyamide. Typical examples of such polymers 1------In accordance with invention. 10 6() () are given above in the section entitled "Component A -do------5 () {) Polyamides.' Especially preferred are the polyamides con ----do. ---- - 2.5 (3) () taining free primary or secondary amino groups. A useful class ... --do----- 1.25 (5) () --do------(). () () of such polymers may be prepared, in known manner, by --do------().5 20 t reacting an aliphatic polyamine such as one of the formula --do------0.25 20 t 8. -----do------0, 125 20 ------Control (No treatment in 10 60 22 Sol. B). (wherein R is a short chain alkylene radical such as -CH 10------Blank (Untreated).------27 CH-and n is 2 to 4) with heat-dimerized, unsaturated, high molecular weight fatty acids. The polyamides of this type are 25 The products of run 1 in accordance with the invention and readily emulsifiable in water and may be applied to the fibrous the control (run 9) were subjected to shrinkage tests before substrate in such form. In this event, component B is preferably applied in solution in an essentially water-immisci and after extraction with isopropanol for 5 hours in a Soxhlet ble, organic solvent such as benzene, toluene, or the like. extraction. The results are given below: Since the highly reactive groups of the preferred class of 30 polyamides are primary or secondary amino groups, com Area shrinkage ponent B is selected to contain complementary reactive Wt. of resin on (Accelerotor), groups, e.g., carbonyl halide, sulphonyl halide, haloformate, fabric percent carbamyl halide, anhydride, or isocyanate. Suitable com Before After ex- Before After ex pounds of these types are given above in the sections listing 35 Run Procedure extraction traction extraction tractioli ------In accordance with 20 20 () the various types of component B. Generally, compounds con invention. taining isocyanate groups are preferred as they not only form ------Control (No treat- 12 0. 22 23.3 the cross-links rapidly but cause no evolution of acid by ment with Sol. B). products (as is the case with acid halide fixatives). 10------Blank (Untreated).------...------27 - - - - Another useful plan for applying the aforesaid polyamides 40 containing free amino groups involves applying the polyamide EXAMPLE XXII to the substrate as a solution in a hydroxylated organic solvent such as ethanol or isopropanol (in which they are easily solu Solution A: The polyamide of example XXI was dissolved in ble). The treated substrate is then dried to remove the solvent isopropanol in concentration of 20 percent. One volume of and the substrate then treated with the isocyanate-containing 45 this solution was poured into 5 volumes of water containing fixative dissolved in a solvent such as benzene or toluene, thus ca. 0.01 percent of nonionic wetting agent, applying vigorous to accomplish the cross-linking at a solid-liquid boundary. agitation to form an emulsion. This emulsion was further This embodiment 4 of the invention is further illustrated diluted to various concentrations as given below. below: 50 Solution B: 2 percent toluene diisocyanate in methyl chloroform. EXAMPLE XX Samples of wool cloth and wool top (wool top is a thick but Component A was a polyamide-a condensation product of very open and loosely assembled strand of wool fibers with no diethylene triamine and heat-dimerized unsaturated (mainly twist) were treated with the solutions as described in example Cus) fatty acids-containing free primary and secondary 55 I, part 3, using the sequence A-B. Tests for shrinkage of the amine groups. An idealized structure of this compound may products are tabulated below: be represented by the following: H2N-CH-CH-NH-CH-CH-NH O O Area shrink- Lengthwise | Conc. of age of shrinkage a sit-on-on-sit-on-on sil 60 polyamide fabric (Ac- of top (Ac in Sol. A celerotor), celerotor), L rocedure percent percent percent wherein O () 0.5 6. 3. 4 I In accordance with invention- 8. 16. 3. -C-R-C- 65 0.06 12.6 3,5 Control (Treated with Sol. B represents the acyl radical of the dimerized fat acid and n is only)------27 5.0 the number of repeating units, usually about 20 to 60 The Control (Treated with Sol. A polyamide had an amine value of 290-320(amine value is the only)------2.0 27 18 milligrams equivalent of KOH per gram of polyamide) and a Blank (Untreated) ------27 25 viscosity in a Brookfield viscometer at 40° C. of 80-120 70 poises. Solution A: The above polyamide in isopropanol at various EXAMPLE XXIII concentrations given below. Solution B: Toluene diisocyanate (4 percent by volume) in Wool top was treated with solutions of various complemen benzene. 75 tary components A and B, using the technique described in ex 3,632,391 35 36 ample I, part 3. The products were tested for shrinkage in the Wool cloth was treated with the above solutions as in exam following manner: The products were gilled to remove any ple I, part 3, using the sequence A-B. fiber-to-fiber bonding which may have occurred during treat The results of tests on the products are given below: ment. The products were then cut to standard length (50 cm.), sewn into a casing of cheesecloth, and given a 15-minute wash Water rebellenty Area in an agitator-type household washing machine. After washing ------v-m------striking Conc. of Wt. of After (Act'irotor, and air-drying, the samples were measured to determine the polysiloxalle resin on Before After Accel- after ex percentage of shrinkage. The components used and the results in Sol. A cloth, extrac- extrac- rotor truction), of the tests are tabulated below: percent percent tion tio wash percent. O 3------SO 10. O) 3. () 1.5------0.5 8) 10) 10) F.8 Sequence Component A Component B Shrinkage Control of and conc. in and conc. in in length, (Untreated). O 50 ------27.) treatlet Sol, A,% Sol. B, 9. Extractiot with benzel, 3 hours i Soxlet extrictor. A*-B. PA, 2 TDi, 3 0.8 15 NoTE. Increase in water repellency, after extraction and after washing A-B PA, TD, 3 2.2 believed due to removal of unreacted hydrophilic materials frolin cloth. A*-B. PA, 0.5 TD, 3 S.S B-A PU, .5 HMDA, 0.5 10 Having thus described our invention, we claim: B-A Ter, .5 HMDA, 0.5 3.0 1. Fibrous material carrying a deposit of a preformed Control --- - 28.5 polymer cross-linked in situ through reaction with a fixative, 20 said preformed polymer being an addition polymerization * Air-dried before entering next solution. product of at least one polymerizable monomer contain 1ng a

Abbreviations: 25 PA = polyamide as described in Ex. XXI, in isopropanol. grouping, said polymer having a molecular weight of at least PU = polyurethane as described in Ex. XIX, in methyl 1,000 and containing in haloformate groups, chloroform. said fixative being a polyamine containing m amino groups, Ter terpolymer of ethylene, vinyl acetate, and in and m each having a value of at least 2, the sum of n and m methacrylyl chloride as described in Ex. I, in methyl 30 being at least 5. chloroform. 2. The product of claim 1 wherein the preformed polymer is TD= toluene diisocyanate in methyl chloroform. a copolymer of (i) a polymerizable monomer containing a HMDA = hexamethylene diamine, in water plus 0.05% nonionic wetting agent. 35 EMBODIMENT 5 grouping and a haloformate group, and (ii) at least one other In accordance with this embodiment, component A is a polymerizable monomer containing a polysiloxane. A particular benefit achieved with such copolymers is the imparting to the fibers of a high degree of 40 water repellency and consequently resistance to soils. Generally, the polysiloxane will contain hydroxy or amine grouping which is free from groups reactive with radicals con radicals as the highly reactive groups and the polymer is taining active hydrogen atoms. preferably applied as a solution (or emulsion) in water. Com 3. Fibrous material carrying a deposit of a preformed ponent B is a compound containing carbonylhalide, sulphonyl 45 polymer cross-linked in situ through reaction with a fixative, halide, haloformate, carbamyl halide, anhydride, or iso said preformed polymer being an addition polymerization cyanate groups (the latter being preferred) and is applied as a product of at least one polymerizable monomer contain solution in an essentially water-immiscible solvent such as 1ng a benzene, toluene, or the like. This embodiment 5 of the invention is further illustrated 50 below: grouping, said polymer having a molecular weight of at least EXAMPLE XXIV 1,000 and containing n isocyanate groups, said fixative being a polyamine containing m amino groups, Component A was a commercial polysiloxane containing 55 in and m each having a value of at least 2, the sum of n and m more than three amino groups per molecule. This polymer had being at least 5. a specific gravity of 0.988 to 1.005 at 25°C., viscosity 100 to 4. The product of claim 3 wherein the preformed polymer is 400 centistokes and contained 5.5 to 6.3 percent free NH2. a copolymer of (i) a polymerizable monomer containing a The repeating unit of the polysiloxane is believed to have the structure 60 CH2-cCK (H, ch, grouping and an isocyanate group, and (ii) at least one other --O-i-o- polymerizable monomer containing a CH3 (gH), 65 NH grouping which is free from groups reactive with radicals con taining active hydrogen atoms. Solution A: The above polysiloxane was stirred into water S. Fibrous material carrying a deposit of a preformed containing added acetic acid to give a pH of about 11 in the 70 polymer cross-linked in situ through reaction with a fixative, resulting milky solution. One solution at a concentration of 3 said preformed polymer being an addition polymerization percent polysiloxane and another at 1.5 percent polysiloxane product of at least one polymerizable monomer contain were thus prepared. ing a Solution B: 2 percent (by volume) of 2,4-toluene diiso cyanate in methyl chloroform. 75 CE - C { 3,632,391 37 38 grouping, said polymer having a molecular weight of at least grouping and an amino group, said polymer having a molecu 1,000 and containing n isocyanate groups, lar weight of at least 1,000 and containing namino groups, said fixative being a polyol containing m hydroxy groups, said fixative containing m groups reactive with radicals con in and m each having a value of at least 2, the sum of n and m taining active hydrogen atoms, being at least 5. in and m each having a value of at least 2, the sum of n and m 6. The product of claim 5 wherein the preformed polymer is being at least 5. a copolymer of (i) a polymerizable monomer containing a 12. The product of claim 11 wherein the fixative is a mul tifunctional isocyanate. 10 13. The product of claim 12 wherein the preformed polymer is a copolymer of (i) a polymerizable monomer con grouping and an isocyanate group, and (ii) at least one other taining a polymerizable monomer containing a Cl2:...C. C. 15 CI-cCK grouping and an amino group, and (ii) at least one other grouping which is free from groups reactive with radicals con polymerizable monomer containing a taining active hydrogen atoms. 7. Fibrous material carrying a deposit of a preformed C-C K polymer cross-linked in situ through reaction with a fixative, 20 said preformed polymer being an addition polymerization grouping which is free from groups reactive with radicals con product of at least one polymerizable monomer contain taining active hydrogen atoms. ing a 14. Fibrous material carrying a deposit of a preformed polymer cross-linked in situ through reaction with a fixative, 25 said preformed polymer being an addition polymerization product of at least one polymerizable monomer contain grouping, said polymer having a molecular weight of at least ing a 1,000 and containing n anhydride groups, said fixative being a polyamine containing m amino groups, in and m each having a value of at least 2, the sum of n and m 30 being at least 5. grouping, and a hydroxyl group said polymer having a molecu 8. The product of claim 7 wherein the preformed polymer is lar weight of at least 1,000 and containing n hydroxyl groups, a copolymer of (i) a polymerizable monomer containing a said fixative containing m groups reactive with radicals con taining active hydrogen atoms, 35 in and m each having a value of at least 2, the sum of n and m being at least 5. grouping and an anhydride group, and (ii) at least one other 15. The product of claim 14 wherein the fixative is a mul polymerizable monomer containing a tifunctional isocyanate. 16. The product of claim 15 wherein the preformed 40 polymer is a copolymer of (i) a polymerizable monomer con taining a grouping which is free from groups reactive with radicals con taining active hydrogen atoms. CII-CK 9. Fibrous material carrying a deposit of a preformed polymer cross-linked in situ through reaction with a fixative, 45 grouping and a hydroxyl group, and (ii) at least one other said preformed polymer being an addition polymerization polymerizable monomer containing a product of at least one polymerizable monomer contain ing a CI-CC 50 grouping which is free from groups reactive with radicals con taining active hydrogen atoms. grouping, said polymer having a molecular weight of at least 17. Fibrous material carrying a deposit of a preformed con l,000 and containing n carbamyl halide groups, densation polymer cross-linked in situ through reaction with a said fixative being a polyamine containing m amino groups, fixative, in and m each having a value of at least 2, the sum of n and m 55 said preformed condensation polymer being a polyester being at least 5. having a molecular weight of at least 1,000 and contain 10. The product of claim 9 wherein the preformed polymer ing in carbonylhalide groups, is a copolymer of (i) a polymerizable monomer containing a said fixative being a polyamine containing m amino groups, n and m each having a value of at least 2, the sum of n and m 60 being at least 5. CH=CC 18. Fibrous material carrying a deposit of a preformed con grouping and a carbamyl halide group, and (ii) at least one densation polymer cross-linked in situ through reaction with a other polymerizable monomer containing a fixative, said preformed condensation polymer being a polyester 65 having a molecular weight of at least 1,000 and contain ing in haloformate groups, grouping which is free from groups reactive with radicals con said fixative being a polyamine containing m amino groups, taining active hydrogen atoms. in and m each having a value of at least 2, the sum of n and m 11. Fibrous material carrying a deposit of a preformed being at least 5. polymer cross-linked in situ through reaction with a fixative, 70 19. Fibrous material carrying a deposit of a preformed con said preformed polymer being an addition polymerization densation polymer cross-linked in situ through reaction with a product of at least one polymerizable monomer contain fixative, said preformed condensation polymer being a polyether ing a having a molecular weight of at least 1,000 and contain ( - (< 75 ing in carbonylhalide groups, 3,632,391 39 40 said fixative being a polyamine containing in amino groups, impregnating the dried fibrous material with a complemen in and m each having a value of at least 2, the sum of n and m tary reactant in a fluid state, being at least 5. one of said reactants being a preformed polymer having a 20. Fibrous material carrying a deposit of a preformed con molecular weight of at least 1,000 and bearing in an densation polymer cross-linked in situ through reaction with a hydride groups, fixative, the other of said reactants being a fixative bearing m amino said preformed condensation polymer being a polyether groups, having a molecular weight of at least 1,000 and contain in and in each having a value of at least 2, the sum of n and m ing n haloformate groups, being at least 5, said fixative being a polyamine containing m amino groups, 1 O the said polymer directly cross-linking with the fixative in and m each having a value of 2, the sum of n and m being under said conditions to form a three-dimensional struc at least 5. ture on the fibrous material. 21. Fibrous material carrying a deposit of a preformed con 26. A process for modifying a fibrous material which com densation polymer cross-linked in situ through reaction with a prises fixative, 5 impregnated a fibrous material with a solution of a reactant said preformed condensation polymer being a polyglycol in a volatile solvent, polyether having a molecular weight of at least 1,000 and drying the treated fibrous material to remove the volatile containing in hydroxyl groups, solvent, and said fixative being a polyisocyanate containing n isocyanate impregnating the dried fibrous material with a complemen groups, tary reactant in a fluid state, in and in each having a value of at least 2, the sum of n and m one of said reactants being a preformed polymer having a being at least 5. molecular weight of at least 1,000 and bearing in amino 22. The product of claim 21 wherein the preformed groups, polyglycol polyether is a polymerization product of a lower al the other of said reactants being a fixative bearing m car kylene oxide and an aliphatic polyol. 25 bonylhalide groups, 23. A process for modifying a fibrous material which com in and m each having a value of at least 2, the sum of n and m prises being at least 5, impregnating a fibrous material with a solution of a reactant the said polymer directly cross-linking with the fixative in a volatile solvent, under said conditions to form a three-dimensional struc drying the treated fibrous material to remove the volatile 30 ture on the fibrous material. solvent, and 27. A process for modifying a fibrous material which con impregnating the dried fibrous material with a complemen prises tary reactantin a fluid state, impregnating a fibrous material with a solution of a reactant one of said reactants being a preformed polymer having a in a volatile solvent, molecular weight of at least 1,000 and bearing in carbonyl 35 drying the treated fibrous material to remove the volatile halide groups, solvent, and the other of said reactants being a fixative bearing m amino impregnating the dried fibrous material with a complemen groups, tary reactant in a fluid state, in and m each having a value of at least 2, the sum of n and m one of said reactants being a preformed polymer having a being at least 5, 40 molecular weight of at least 1,000 and bearing in amino the said polymer directly cross-linking with the fixative groups, under said conditions to form a three-dimensional struc the other of said reactants being a fixative bearing m ture on the fibrous material. haloformate groups, 24. A process for modifying a fibrous material which com n and m each having a value of at least 2, the sum of n and m prises 45 being at least 5, impregnating a fibrous material with a solution of a reactant the said polymer directly cross-linking with the fixative in a volatile solvent, under said conditions to form a three-dimensional struc drying the treated fibrous material to remove the volatile ture on the fibrous material. solvent, and 28. A process for modifying a fibrous material which com impregnating the dried fibrous material with a complemen 50 prises tary reactant in a fluid state, impregnating a fibrous material with a solution of a reactant one of said reactants being a preformed polymer having a in a volatile solvent, molecular weight of at least 1,000 and bearing n halofor drying the treated fibrous material to remove the volatile mate groups, solvent, and the other of said reactants being a fixative bearing m amino 55 impregnating the dried fibrous material with a complemen groups, tary reactant in a fluid state, in and m each having a value of at least 2, the sum of n and in one of said reactants being a preformed polymer having a being at least 5, molecular weight of at least 1,000 and bearing in amino the said polymer directly cross-linking with the fixative groups, under said conditions to form a three-dimensional struc 60 the other of said reactants being a fixative bearing man ture on the fibrous material. hydride groups, 25. A process for modifying a fibrous material which com in and m each having a value of at least 2, the sum of n and m prises being at least 5, impregnating a fibrous material with a solution of a reactant the said polymer directly cross-linking with the fixative in a volatile solvent, 65 under said conditions to form a three-dimensional struc drying the treated fibrous material to remove the volatile ture on the fibrous material. solvent, and ; : . . .

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